Branched Ethylene Polymers Produced via Use of Vinyl Transfer Agents and Processes for Production Thereof

ABSTRACT

This invention relates to the use of pyridyldiamido and/or quinolinyldiamido transition metal complexes and catalyst systems with an activator and a metal hydrocarbenyl chain transfer agent, such as an aluminum vinyl-transfer agent (AVTA), to produce branched ethylene copolymers, preferably ethylene-butene, ethylene-hexene and ethylene-octene copolymers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of U.S. Ser. No.62/465,629, filed Mar. 1, 2017 and is incorporated by reference in itsentirety.

This invention relates to U.S. Ser. No. 62/212,405, filed Aug. 31, 2015;U.S. Ser. No. 62/332,940, filed May 6, 2016; U.S. Ser. No. 62/332,921,filed May 6, 2016; and U.S. Ser. No. 15/629,586, filed Jun. 21, 2017.

FIELD OF THE INVENTION

This invention relates to the use of pyridyldiamido and/orquinolinyldiamido transition metal complexes and catalyst systems withan activator and a metal hydrocarbenyl chain transfer agent, such as analuminum vinyl-transfer agent (AVTA), to produce branched ethylene basedpolymers.

BACKGROUND OF THE INVENTION

Pyridyldiamido transition metal complexes are disclosed in US2015/0141601; US 2014/0316089; US 2012/0071616; US 2011/0301310; US2011/0224391; and US 2010/0022726, where such complexes are useful ascatalyst components for the polymerization of olefins.

US 2015/0141596; US 2015/0141590; and US 2014/0256893 describe theproduction of polyolefins using pyridyldiamido catalysts in the presenceof chain-transfer agents that do not feature transferrable vinyl groups.

Macromolecules 2002, 35, 6760-6762 discloses propene polymerization withtetrakis(pentafluorophenyl)borate, 7-octenyldiisobutylaluminum, andracMe₂Si(2-Me-indenyl)₂ZrCl₂ or Ph₂C(cyclopentadienyl)(fluorenyl)ZrCl₂to produce polypropylene with octenyldiisobutylaluminum incorporated asa comonomer.

Japanese. Kokai Tokkyo Koho (2004), JP 2004-83773-A describes thepreparation of polypropylene in the presence of trialkenylaluminum usingmetallocene and Ziegler-Natta catalysts.

Macromolecules 1995, 28, 437-443 describes the formation of isotacticpolypropylene containing vinyl end groups by the Ziegler-Natta catalyzedpolymerization of propylene in the presence of dialkenylzincs.

Macromolecules 2002, 35, 3838-3843 describes the formation of long-chainbranched polypropylene via the insertion of in situ formedvinyl-terminated polypropylene into growing polymer chains.

Macromolecules 2002, 35, 9586-9594 describes the formation of long-chainbranched copolymers of ethylene and alpha olefins via the insertion ofin situ formed vinyl-terminated polymer into growing polymer chains.

Eur. Pat. Appl. (2012), EP 2436703 Al describes the production of combarchitecture branch block copolymers in a process that uses dualcatalysts and a zinc-based polymerizable chain shuttling agent.

WO 2007/035492 describes the production of long-chain branched andbranch block copolymers by polymerization of alkene monomers in thepresence of a zinc-based polymerizable shuttling agent.

WO 2016/102690 discloses preparation of branched polyolefin using ametal hydrocarbyl chain transfer agent.

References of interest also include: 1) Vaughan, A; Davis, D. S.;Hagadorn, J. R. in Comprehensive Polymer Science, Vol. 3, Chapter 20,“Industrial catalysts for alkene polymerization”; 2) Gibson, V. C.;Spitzmesser, S. K. Chem. Rev. 2003, 103, 283; and 3) Britovsek, G. J.P.; Gibson, V. C.; Wass, D. F. Angew. Chem. Int. Ed. 1999, 38, 428; 4)US 2002/0142912; 5) U.S. Pat. No. 6,900,321; 6) U.S. Pat. No. 6,103,657;7) WO 2005/095469; 8) US 2004/0220050A1; 9) WO 2007/067965; 10) Froese,R. D. J. et al., J. Am. Chem. Soc. 2007, 129, pp. 7831-7840; 11) WO2010/037059; 12) US 2010/0227990 A1; 13) WO 2002/38628 A2; 14) US2014/0256893; 15) Guerin, F.; McConville, D. H.; Vittal, J. J.,Organometallics, 1996, 15, p. 5586.

There is still a need in the art for new and improved catalyst systemsfor the polymerization of olefins, in order to achieve specific polymerproperties, such as long chain branching, high vinyl content, toincrease conversion or comonomer incorporation, or to alter comonomerdistribution.

SUMMARY OF THE INVENTION

This invention relates to processes to produce branched ethylenecopolymers comprising:

1) contacting monomer comprising ethylene and C₄ to C₈ alpha-olefincomonomers (preferably C₆) with a catalyst system comprising anactivator, a metal hydrocarbenyl chain transfer agent (such as analuminum vinyl transfer agent), and one or more single site catalystcomplexes, such as pyridyldiamido or quinolinyldiamido complexesrepresented by the Formula I or II;

-   wherein:-   M is a Group 3, 4, 5, 6, 7, 8, 9, or 10 metal;-   E is chosen from C(R²) or C(R³)(R³′);-   X is an anionic leaving group;-   L is a neutral Lewis base;-   R¹ and R¹³ are independently selected from the group consisting of    hydrocarbyls, substituted hydrocarbyls, and silyl groups;-   R² is a group containing 1-10 carbon atoms that is optionally joined    with R⁴ to form an aromatic ring;-   R³, R³′, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each    independently selected from the group consisting of hydrogen,    hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted    hydrocarbyls, halogen, and phosphino;-   J is a divalent group that forms a three-atom-length bridge between    the pyridine ring and the amido nitrogen;-   n is 1 or 2;-   m is 0, 1, or 2;-   two X groups may be joined together to form a dianionic group;-   two L groups may be joined together to form a bidentate Lewis base;-   an X group may be joined to an L group to form a monoanionic    bidentate group;-   adjacent groups from the following R³, R³′, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,    R¹⁰, R¹¹, and R¹² may be joined to form a ring; and-   2) obtaining branched copolymers comprising at least 50 mol %    ethylene, one or more C₄ to C₈ alpha-olefin comonomers (preferably    C₆), and a remnant of the metal hydrocarbenyl chain transfer agent,    wherein said branched ethylene copolymer: a) has a g′_(vis) of less    than 0.97; b) is essentially gel free (such as 5 wt % or less of    xylene insoluble material); c) has an Mw of 60,000 g/mol or more;    and d) has a Mw/Mn of less than 4.0.

This invention also relates to processes where the metal hydrocarbenylchain transfer agent in the above catalyst systems is one or morealuminum vinyl transfer agents (AVTA) represented by Formula:

Al(R′)_(3−v)(R″)_(v)

-   wherein each R′, independently, is a C₁-C₃₀ hydrocarbyl group; each    R″, independently, is a C₄-C₂₀ hydrocarbenyl group having an    end-vinyl group; and v is from 0.1 to 3.

This invention further relates to novel branched ethylene copolymerscomprising from about 50 to 99 mol % ethylene, from 1 to 50 mol % C₄(preferably C₆) to C₈ alpha-olefin comonomers, and a remnant of themetal hydrocarbenyl chain transfer agent, wherein said branched ethylenecopolymer: a) has a g′_(vis) of less than 0.97; b) is essentially gelfree (such as 5 wt % or less of xylene insoluble material); c) has an Mwof 60,000 g/mol or more; and d) has a Mw/Mn of less than 4.0.

BRIEF DESCRIPTION OF THE FIGURE

The figure is a drawing of the reaction of iBu₂AlH and 1,7 octadiene atvarious conditions. Compounds 1 and 2 represent average compositions ashydrocarbyl and hydrocarbenyl groups may exchange between Al centers.Triene product 3 may be a mixture of similar molecules containing avinylidene group.

DETAILED DESCRIPTION OF THE INVENTION Definitions

This invention relates processes to produce ethylene copolymers usingtransition metal complexes and catalyst systems that include thetransition metal complexes. The term complex is used to describemolecules in which an ancillary ligand is coordinated to a centraltransition metal atom. The ligand is bulky and stably bonded to thetransition metal so as to maintain its influence during use of thecatalyst, such as polymerization. The ligand may be coordinated to thetransition metal by covalent bond and/or electron donation coordinationor intermediate bonds. The transition metal complexes are generallysubjected to activation to perform their polymerization oroligomerization function using an activator which is believed to createa cation as a result of the removal of an anionic group, often referredto as a leaving group, from the transition metal.

As used herein, the numbering scheme for the Periodic Table groups isthe new notation as set out in Chemical and Engineering News, 63(5), 27(1985).

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing Formula: P/(T×W) and expressed in units of gPgcat⁻¹hr⁻¹.Conversion is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor. Catalyst activityis a measure of how active the catalyst is and is reported as the massof product polymer (P) produced per mole of catalyst (cat) used(kgP/molcat).

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, the olefin present in such polymer or copolymer is thepolymerized form of the olefin. For example, when a copolymer is said tohave an “ethylene” content of 35 wt % to 55 wt %, it is understood thatthe mer unit in the copolymer is derived from ethylene in thepolymerization reaction and said derived units are present at 35 wt % to55 wt %, based upon the weight of the copolymer. A “polymer” has two ormore of the same or different mer units. A “homopolymer” is a polymerhaving mer units that are the same. A “copolymer” is a polymer havingtwo or more mer units that are different from each other. A “terpolymer”is a polymer having three mer units that are different from each other.“Different” as used to refer to mer units indicates that the mer unitsdiffer from each other by at least one atom or are differentisomerically. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. An oligomer is typically a polymerhaving a low molecular weight, such as an Mn of less than 25,000 g/mol,or in an embodiment less than 2,500 g/mol, or a low number of mer units,such as 75 mer units or less or 50 mer units or less. An “ethylenepolymer” or “ethylene copolymer” is a polymer or copolymer comprising atleast 50 mol % ethylene derived units, a “propylene polymer” or“propylene copolymer” is a polymer or copolymer comprising at least 50mol % propylene derived units, and so on.

For the purposes of this invention, ethylene shall be considered anα-olefin.

For purposes of this invention and the claims thereto, when a polymer isreferred to as comprising a metal hydrocarbenyl chain transfer agent,the metal hydrocarbenyl chain transfer agent present in such polymer orcopolymer is the polymerized portion of the metal hydrocarbenyl chaintransfer agent, also referred to as the remnant of the metalhydrocarbenyl chain transfer agent. The remnant of a metal hydrocarbenylchain transfer agent is defined to be the portion of the metalhydrocarbenyl chain transfer agent containing an allyl chain end thatbecomes incorporated into the polymer backbone. For example if the allylchain end of the metal hydrocarbenyl chain transfer agent isCH₂═CH—(CH₂)₆, the sp² carbons of the metal hydrocarbenyl chain transferagent become a part of the polymer backbone and the —(CH₂)₆, becomes apart of a side chain.

For purposes of this invention and claims thereto, the term“substituted” means that a hydrogen group has been replaced with aheteroatom, or a heteroatom-containing group. For example, a“substituted hydrocarbyl” is a radical made of carbon and hydrogen whereat least one hydrogen is replaced by a heteroatom orheteroatom-containing group.

A metallocene catalyst is defined as an organometallic compound with atleast one π-bound cyclopentadienyl moiety (or substitutedcyclopentadienyl moiety) and more frequently two π-boundcyclopentadienyl moieties or substituted cyclopentadienyl moieties.

As used herein, M_(n) is number average molecular weight, M_(w) isweight average molecular weight, and M_(z) is z average molecularweight, wt % is weight percent, and mol % is mole percent. Molecularweight distribution (MWD), also referred to as polydispersity index(PDI), is defined to be M_(w) divided by M_(n). Unless otherwise noted,all molecular weight units (e.g., M_(w), M_(n), M_(z)) are g/mol.

Unless otherwise noted all melting points (T_(m)) are DSC second melt.

The following abbreviations may be used herein: dme is1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr ispropyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, cPR iscyclopropyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu ispara-tertiary butyl, nBu is normal butyl, sBu is sec-butyl, TMS istrimethylsilyl, TIBAL is triisobutylaluminum, TNOAL istri(n-octyl)aluminum, MAO is methylalumoxane, p-Me is para-methyl, Ph isphenyl, Bn is benzyl (i.e., CH₂Ph), THF (also referred to as the istetrahydrofuran, RT is room temperature (and is 23° C. unless otherwiseindicated), tol is toluene, EtOAc is ethyl acetate, Cy is cyclohexyl andAVTA is an aluminum-based vinyl transfer agent.

A “catalyst system” comprises at least one catalyst compound and atleast one activator. When “catalyst system” is used to describe such thecatalyst compound/activator combination before activation, it means theunactivated catalyst complex (pre-catalyst) together with an activatorand, optionally, a co-activator. When it is used to describe thecombination after activation, it means the activated complex and theactivator or other charge-balancing moiety. The transition metalcompound may be neutral as in a pre-catalyst, or a charged species witha counter ion as in an activated catalyst system. For the purposes ofthis invention and the claims thereto, when catalyst systems aredescribed as comprising neutral stable forms of the components, it iswell understood by one of ordinary skill in the art, that the ionic formof the component is the form that reacts with the monomers to producepolymers.

In the description herein, the catalyst may be described as a catalystprecursor, pre-catalyst compound, catalyst compound, transition metalcomplex, or transition metal compound, and these terms are usedinterchangeably. A polymerization catalyst system is a catalyst systemthat can polymerize monomers to polymer. An “anionic ligand” is anegatively charged ligand which donates one or more pairs of electronsto a metal ion. A “neutral donor ligand” is a neutrally charged ligandwhich donates one or more pairs of electrons to a metal ion. Activatorand cocatalyst are also used interchangeably.

A scavenger is a compound that is typically added to facilitatepolymerization by scavenging impurities. Some scavengers may also act asactivators and may be referred to as co-activators. A co-activator, thatis not a scavenger, may also be used in conjunction with an activator inorder to form an active catalyst. In some embodiments a co-activator canbe pre-mixed with the transition metal compound to form an alkylatedtransition metal compound.

Non-coordinating anion (NCA) is defined to mean an anion either thatdoes not coordinate to the catalyst metal cation or that does coordinateto the metal cation, but only weakly. The term NCA is also defined toinclude multicomponent NCA-containing activators, such asN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain anacidic cationic group and the non-coordinating anion. The term NCA isalso defined to include neutral Lewis acids, such astris(pentafluorophenyl)boron, that can react with a catalyst to form anactivated species by abstraction of an anionic group. An NCA coordinatesweakly enough that a neutral Lewis base, such as an olefinically oracetylenically unsaturated monomer can displace it from the catalystcenter. Any metal or metalloid that can form a compatible, weaklycoordinating complex may be used or contained in the noncoordinatinganion. Suitable metals include, but are not limited to, aluminum, gold,and platinum. Suitable metalloids include, but are not limited to,boron, aluminum, phosphorus, and silicon. Activators containingnon-coordinating anions can also be referred to as stoichiometricactivators. A stoichiometric activator can be either neutral or ionic.The terms ionic activator and stoichiometric ionic activator can be usedinterchangeably. Likewise, the terms neutral stoichiometric activatorand Lewis acid activator can be used interchangeably. The termnon-coordinating anion activator includes neutral stoichiometricactivators, ionic stoichiometric activators, ionic activators, and Lewisacid activators.

For purposes of this invention and claims thereto in relation tocatalyst compounds, the term “substituted” means that a hydrogen grouphas been replaced with a hydrocarbyl group, a heteroatom, or aheteroatom-containing group. For example, methyl cyclopentadiene (Cp) isa Cp group substituted with a methyl group.

For purposes of this invention and claims thereto, “alkoxides” includethose where the alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl groupmay be straight chain, branched, or cyclic. The alkyl group may besaturated or unsaturated. In some embodiments, the alkyl group maycomprise at least one aromatic group.

The terms “hydrocarbyl radical,” “hydrocarbyl,” “hydrocarbyl group,”“alkyl radical,” and “alkyl” are used interchangeably throughout thisdocument. Likewise, the terms “group,” “radical,” and “substituent” arealso used interchangeably in this document. For purposes of thisdisclosure, “hydrocarbyl radical” is defined to be C1-C100 radicals,that may be linear, branched, or cyclic, and when cyclic, aromatic ornon-aromatic. Examples of such radicals include, but are not limited to,methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cyclooctyl, and the like including theirsubstituted analogues. Substituted hydrocarbyl radicals are radicals inwhich at least one hydrogen atom of the hydrocarbyl radical has beensubstituted with at least one halogen (such as Br, Cl, F or I) or atleast one functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂,SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like, or where atleast one heteroatom has been inserted within a hydrocarbyl ring.

The term “alkenyl” or “hydrocarbenyl” means a straight-chain,branched-chain, or cyclic hydrocarbon radical having one or more doublebonds that are not part of an aromatic ring. These alkenyl radicals may,optionally, be substituted. Examples of alkenyl radicals include, butare not limited to, ethenyl, propenyl, allyl, 1,4-butadienylcyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl,and the like, including their substituted analogues.

The term “alkoxy” or “alkoxide” means an alkyl ether or aryl etherradical wherein the term alkyl is as defined above. Examples of suitablealkyl ether radicals include, but are not limited to, methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,phenoxyl, and the like.

The term “aryl” or “aryl group” means a six carbon aromatic ring and thesubstituted variants thereof, including but not limited to, phenyl,2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means anaryl group where a ring carbon atom (or two or three ring carbon atoms)has been replaced with a heteroatom, preferably N, O, or S. As usedherein, the term “aromatic” also refers to pseudoaromatic heterocycleswhich are heterocyclic substituents that have similar properties andstructures (nearly planar) to aromatic heterocyclic ligands, but are notby definition aromatic; likewise the term aromatic also refers tosubstituted aromatics.

Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist(e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to onemember of the group (e.g., n-butyl) shall expressly disclose theremaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in thefamily Likewise, reference to an alkyl, alkenyl, alkoxide, or aryl groupwithout specifying a particular isomer (e.g., butyl) expressly disclosesall isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).

The term “ring atom” means an atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring atoms andtetrahydrofuran has 5 ring atoms.

A heterocyclic ring is a ring having a heteroatom in the ring structureas opposed to a heteroatom substituted ring where a hydrogen on a ringatom is replaced with a heteroatom. For example, tetrahydrofuran is aheterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatomsubstituted ring.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn.

A solution polymerization means a polymerization process in which thepolymer is dissolved in a liquid polymerization medium, such as an inertsolvent or monomer(s) or their blends. A solution polymerization istypically homogeneous. A homogeneous polymerization is one where thepolymer product is dissolved in the polymerization medium. Such systemsare preferably not turbid as described in J. Vladimir Oliveira, C.Dariva and J. C. Pinto, Ind. Eng. Chem. Res., 29, 2000, 4627.

A bulk polymerization means a polymerization process in which themonomers and/or comonomers being polymerized are used as a solvent ordiluent using little or no inert solvent as a solvent or diluent. Asmall fraction of inert solvent might be used as a carrier for catalystand scavenger. A bulk polymerization system contains less than 25 wt %of inert solvent or diluent, preferably less than 10 wt %, preferablyless than 1 wt %, preferably 0 wt %.

Process

This invention relates to processes to produce branched ethylenecopolymers comprising:

-   1) contacting monomer comprising ethylene and one or more C₄ to C₈    alpha-olefin monomer (preferably C6) with a catalyst system    comprising an activator (such as an alumoxane or non-coordinating    anion activator), a metal hydrocarbenyl chain transfer agent    (preferably an aluminum vinyl transfer agent), and one or more    single site catalyst complexes, such as a pyridyldiamido or    quinolinyldiamido complex represented by the Formula I or II:

-   wherein:-   M is a Group 3, 4, 5, 6, 7, 8, 9, or 10 metal (preferably M is Zr or    Hf);-   E is chosen from C(R²) or C(R³)(R³′);-   X is an anionic leaving group (preferably X is methyl, chloride, or    dialkylamido);-   L is a neutral Lewis base (preferably L is ether, amine, phosphine,    or thioether);-   R¹ and R¹³ are independently selected from the group consisting of    hydrocarbyls, substituted hydrocarbyls, and silyl groups (preferably    R¹ & R¹³ are aryl groups, preferably R¹ is 2,6-disubstituted aryl,    preferably R¹ is 2,6-diisopropylphenyl, preferably R¹³ is    2-substituted aryl, preferably R¹³ is phenyl, preferably R¹ is    2,6-disubstituted aryl group and R¹³ is an aryl group lacking    substitution in the 2 and 6 positions);-   R² is a group containing 1-10 carbon atoms that is optionally joined    with R⁴ to form an aromatic ring (preferably R² & R⁴ are joined with    the joined R²R⁴ group being CHCHCH);-   R³, R³′, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each    independently selected from the group consisting of hydrogen,    hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted    hydrocarbyls, halogen, and phosphino (preferably R³ & R³′ are    hydrogen);

J is a divalent group that forms a three-atom-length bridge between thepyridine ring and the amido nitrogen (preferably J is selected from thefollowing structures);

-   n is 1 or 2;-   m is 0, 1, or 2; and-   two X groups may be joined together to form a dianionic group;-   two L groups may be joined together to form a bidentate Lewis base;-   an X group may be joined to an L group to form a monoanionic    bidentate group;-   adjacent groups from the following R³, R³′, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,    R¹⁰, R¹¹, and R¹² may be joined to form a ring (preferably R⁷ & R⁸    are joined to form an aromatic ring, preferably R⁷ & R⁸ are joined    with the joined R⁷R⁸ group being CHCHCHCH, preferably R¹⁰ & R¹¹ are    joined to form a five- or six-membered ring, preferably R¹⁰ & R¹¹    are joined, with the joined R¹⁰R¹¹ group being CH₂CH₂ or CH₂CH₂CH₂);-   where the metal hydrocarbenyl chain transfer agent is represented by    the Formula: Al(R′)_(3−v)(R″)_(v) or E[Al(R′)_(2−y)(R″)_(y)]₂,    wherein each R′, independently, is a C₁ to C₃₀ hydrocarbyl group;    each R″, independently, is a C₄ to C₂₀ hydrocarbenyl group having an    allyl chain end; E is a group 16 element (such as O or S); v is from    0.01 to 3 (such as 1 or 2), and y is from 0.01 to 2, such as 1 or 2    (preferably the metal hydrocarbenyl chain transfer agent is an    aluminum vinyl-transfer agent (AVTA) represented by the Formula:    Al(R′)_(3-v)(R″)_(v) with R″ defined as a hydrocarbenyl group    containing 4 to 20 carbon atoms and featuring an allyl chain end, R′    defined as a hydrocarbyl group containing 1 to 30 carbon atoms, and    v is 0.1 to 3 (such as 1 or 2)); and-   2) obtaining branched ethylene copolymers comprising at least 50 mol    % ethylene (preferably at least 70 mol % or more, preferably at    least 90 mol % or more), one or more C₄ (preferably C₆) to C₈    alpha-olefin comonomers (preferably 50 mol % or less, preferably 30    mol % or less, preferably from 0.5 to 30 mol %, preferably 1 to 25    mol %, preferably 1 to 15 mol %), and a remnant of the metal    hydrocarbenyl chain transfer agent (preferably from 0.001 to 10 mol    %, alternatively from 0.01 to 5 mol %, alternatively 0.01 to 2 mol    %, alternatively 0.01 to 1 mol %), wherein said branched ethylene    copolymer: a) has a g′_(vis) of less than 0.97 (preferably 0.95 or    less, alternatively 0.92 or less, alternatively 0.90 or less,    alternatively, 0.88 or less, alternatively 0.85 or less,    alternatively 0.80 or less, alternatively 0.70 or less,    alternatively 0.65 or less); b) is essentially gel free (such as 5    wt % or less of xylene insoluble material, alternatively 4 wt % or    less, alternatively 3 wt % or less, alternatively 2 wt % or less,    alternatively 1 wt % or less, alternatively 0 wt %); c) has an Mw of    60,000 g/mol or more (preferably 80,000 or more, alternatively    100,000 or more, alternatively 120,000 or more, alternatively    150,000 or more); and d) has an Mw/Mn of 4.0 or less (preferably 3.5    or less, alternatively 3.0 or less, alternatively 2.5 or less,    alternatively 2.2 or less, alternatively from 2.0 to 3.4).

The catalyst/activator combinations are formed by combining thetransition metal complex with activators in any manner known from theliterature, including by supporting them for use in slurry or gas phasepolymerization. The catalyst/activator combinations may also be added toor generated in solution polymerization or bulk polymerization (in themonomer). The metal hydrocarbenyl chain transfer agent (preferably analuminum vinyl transfer agent) may be added to the catalyst and oractivator before, during or after the activation of the catalyst complexor before or during polymerization. Typically, the metal hydrocarbenylchain transfer agent (preferably the aluminum vinyl-transfer agent) isadded to the polymerization reaction separately, such as before, thecatalyst/activator pair.

The polymer produced from the polymerization using the catalyst systemsdescribed herein preferably contains at least 0.05 allyl chain ends perpolymer chain, 0.1 allyl chain ends per polymer chain, at least 0.2allyl chain ends per polymer chain, at least 0.3 allyl chain ends perpolymer chain, at least 0.4 allyl chain ends per polymer chain, at least0.5 allyl chain ends per polymer chain, at least 0.6 allyl chain endsper polymer chain, at least 0.7 allyl chain ends per polymer chain, atleast 0.8 allyl chain ends per polymer chain, at least 0.8 allyl chainends per polymer chain, at least 1.0 allyl chain ends per polymer chain.Ethylene copolymers are particularly preferred products. If the catalystcomplex chosen is also capable of incorporating bulky alkene monomers,such as C₆ to C₂₀ alpha olefins, into the growing polymer chain, thenthe resulting polymer may contain long chain branches formed by theinsertion of an allyl terminated polymer chain formed in situ (alsoreferred to as a “vinyl-terminated macromonomer”) into the growingpolymer chains. Process conditions including residence time, the ratioof monomer to polymer in the reactor, and the ratio of transfer agent topolymer will affect the amount of long chain branching in the polymer,the average length of branches, and the type of branching observed. Avariety of branching types may be formed, which include combarchitectures and branch on branch structures similar to those found inlow-density polyethylene. The combination of chain growth andvinyl-group insertion may lead to polymer with a branched structure andhaving one or fewer vinyl unsaturations per polymer molecule. Theabsence of significant quantities of individual polymer moleculescontaining greater than one vinyl unsaturation prevents or reduces theformation of unwanted crosslinked polymers. Polymers having long chainbranching typically have a g′vis of 0.97 or less, alternately 0.95 orless, alternately 0.90 or less, alternately 0.85 or less, alternately0.80 or less, alternately 0.75 or less, alternately 0.70 or less,alternately 0.60 or less.

If the catalyst chosen is poor at incorporating comonomers such as C₂ toC₂₀ alpha olefins, then the polymer obtained is largely linear (littleor no long chain branching).

Likewise, process conditions including the ratio of transfer agent topolymer will affect the molecular weight of the polymer. Polymers havinglittle or no long chain branching typically have a g′vis of more than0.97, alternately 0.98 or more.

Alkene polymerizations and co-polymerizations using one or more transferagents, such as an AVTA, with two or more catalysts are also ofpotential use. Desirable products that may be accessed with thisapproach includes polymers that have branch block structures and/or highlevels of long-chain branching.

The transfer agent to catalyst complex equivalence ratio can be fromabout 1:100 to 500,000:1. Preferably, the molar ratio of transfer agentto catalyst complex is greater than one. Alternately, the molar ratio oftransfer agent to catalyst complex is greater than 30:1. Preferably, thetransfer agent is an aluminum vinyl transfer agent (AVTA) and the AVTAto catalyst complex equivalence ratio can be from about 1:100 to500,000:1. Preferably the molar ratio of AVTA to catalyst complex isgreater than one. More preferred the molar ratio of AVTA to catalystcomplex is greater than 30:1.

The AVTA can also be used in combination with other chain transferagents that are typically used as scavengers, such as trialkylaluminumcompounds (where the alkyl groups are selected from C₁ to C₂₀ alkylgroups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof). Usefullythe ATVA can be used in combination with a trialkyl aluminum compoundsuch as tri-n-octylaluminum and triisobutylaluminum. The ATVA can alsobe used in combination with a dialkyl zinc compound, such asdiethylzinc, dimethylzinc, or dipropylzinc.

The transfer agent can also be used in combination withoxygen-containing organoaluminums such as bis(diisobutylaluminum)oxide,MMAO-3A, and other alumoxanes. Certain of these oxygen-containingorganoaluminums are expected to serve as scavengers while remainingsignificantly less prone to hydrocarbyl group chain-transfer thantypical organoaluminums, such as trimethylaluminum ortri(n-octyl)aluminum.

The production of di-end-functionalized polymers is possible with thistechnology. One product, prior to exposure to air, from an alkenepolymerization performed in the presence of AVTA is the aluminum-cappedspecies Al(R′)_(3−v)(polymer-CH═CH₂)_(v), where v is 0.1 to 3(alternately 1 to 3, alternately 1, 2, or 3). The Al-carbon bonds willreact with a variety of electrophiles (and other reagents), such asoxygen, halogens, carbon dioxide, and the like. Thus, quenching thereactive polymer mixture with an electrophile prior to exposure toatmosphere would yield a di-end-functionalized product of the generalFormula: Z-(monomers)_(n)-CH═CH₂, where Z is a group from the reactionwith the electrophile and n is an integer, such as from 1 to 1,000,000,alternately from 2 to 50,000, alternately from 10 to 25,000. Forexample, quenching with oxygen yields a polymer functionalized at oneend with a hydroxy group and at the other end with a vinyl group.Quenching with bromine yields a polymer functionalized at one end with aBr group and at the other end with a vinyl group.

Functional group terminated polymers can also be produced usingfunctional group transfer agents (FGTA). In this embodiment of theinvention, the FGTA is represented by the FormulaM^(FGTA)(R′)_(3−v)(FG)_(v), with R′ and v defined as above, M^(FGTA) aGroup 13 element (such as B or Al), and with FG defined as a groupcontaining 1 to 20 carbon atoms and a functional group Z. The choice ofFG is such that it is compatible with the catalyst system being used.Preferred Z groups include, but are not limited to, non-vinyl olefinicgroups such as vinylidene, vinylene or trisubstitued olefins, cyclicscontaining unsaturation such as cyclohexene, cyclooctene, vinylcyclohexene, aromatics, ethers, and metal-capped alkoxides.

In another embodiment of the invention, the polymer products of thisinvention are of the Formula: polymer-(CH₂)_(n)CH═CH₂ where n is from 2to 18, preferably from 6 to 14, more preferably 6, and where “polymer”is the attached polymeryl chain. Polymers of this Formula areparticularly well suited in making branch polymer combs. The polymercombs can be made by any number of methods. One method would be to use acatalyst system to make the vinyl terminated polymer, and then use asecond catalyst system to incorporate the vinyl terminated polymer intoa polymer backbone made from the second catalyst. This can be donesequentially in one reactor by first making the vinyl terminated polymerand then adding a second catalyst and, optionally, different monomerfeeds in the same reactor. Alternatively, two reactors in series can beused where the first reactor is used to make the vinyl terminatedpolymer which flows into a second reactor in series having the secondcatalyst and, optionally, different monomer feeds. The vinyl terminatedpolymer can be a soft material, as in an ethylene alpha-olefin copolymer(such as ethylene-propylene copolymer), low density polyethylene, or apolypropylene, or a harder material, as in an isotactic polypropylene,high density polyethylene, or other polyethylene. Typically, if thevinyl terminated polymer is soft, it is useful if the polymer backboneof the comb is hard; if the vinyl terminated polymer is hard, it isuseful the polymer backbone of the comb is soft, however any combinationof polymer structures and types can be used.

In another embodiment of the invention, the vinyl-terminated polymers(VTPs) of this invention are of Formula: polymer-(CH₂)_(n)CH═CH₂ where nis from 2 to 18, preferably from 6 to 14, more preferably 6 or 8, andwhere “polymer” is the attached polymeryl chain. VTPs of this Formulaare particularly well suited in making branch block polymers. The branchblock polymers can be made by any number of methods. One method involvesusing the same catalyst that is used to make the VTP, and then changingpolymerization conditions (such as, but not limited to, by changingmonomer composition and/or type and/or the amount or presence of AVTA)in the same or different reactor (such as two or more reactors inseries). In this case, the branch will have a different polymericcomposition vs. the polymer backbone created under the differentpolymerization conditions. Another method would be to use a catalystsystem to make the VTP, then use a second catalyst system to incorporatethe VTPs into a polymer backbone made from the second catalyst. This canbe done sequentially in one reactor by first making the VTP and thenadding a second catalyst and, optionally, different monomer feeds in thesame reactor. Alternatively, two reactors in series can be used wherethe first reactor is used to make the VTP which flows into a secondreactor in series having the second catalyst and, optionally, differentmonomer feeds. The branched block polymers can be of any composition,however, typically a combination of soft and hard polymers (relative toone another) are preferred.

Useful metal hydrocarbenyl chain transfer agents (preferably thealuminum vinyl transfer agents) are typically present at from 10 or 20or 50 or 100 equivalents to 600 or 700 or 800 or 1000 equivalentsrelative to the catalyst complex. Alternately, the metal hydrocarbenylchain transfer agents are present at a catalyst complex-to-transferagent molar ratio of from about 1:3000 to 10:1; alternatively 1:2000 to10:1; alternatively 1:1000 to 10:1; alternatively, 1:500 to 1:1;alternatively 1:300 to 1:1; alternatively 1:200 to 1:1; alternatively1:100 to 1:1; alternatively 1:50 to 1:1; alternatively 1:10 to 1:1.

In any embodiment of this invention where the aluminum vinyl transferagent is present, the aluminum vinyl transfer agent is present at acatalyst complex-to-aluminum vinyl transfer agent molar ratio of fromabout 1:3000 to 10:1; alternatively 1:2000 to 10:1; alternatively 1:1000to 10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1;alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; alternatively1:50 to 1:1; alternatively 1:10 to 1:1, alternately from 1:1000 or more.

Transition Metal Complex

Transition metal complexes useful herein are certain “non-metallocene”olefin polymization catalysts that undergo alkyl group transfer with theAVTA at a rate that is much higher than the rate at which they undergotypical termination processes, such as beta hydride elimination orchain-transfer to monomer. The term “non-metallocene catalyst”, alsoknown as “post-metallocene catalyst” describe transition metal complexesthat do not feature any pi-coordinated cyclopentadienyl anion donors (orthe like) and are useful the polymerization of olefins when combinedwith common activators.

Particularly useful single site catalyst complexes includepyridyldiamido and quinolinyldiamido complexes represented by theFormulae I and II:

-   wherein:-   M is a Group 3, 4, 5, 6, 7, 8, 9, or 10 metal (preferably M is Zr or    Hf);-   E is chosen from C(R²) or C(R³)(R³′);-   X is an anionic leaving group (preferably X is methyl, chloride, or    dialkylamido);-   L is a neutral Lewis base (preferably L is ether, amine, phosphine,    or thioether);-   R¹ and R¹³ are independently selected from the group consisting of    hydrocarbyls, substituted hydrocarbyls, and silyl groups (preferably    R¹ & R¹³ are aryl groups, preferably R¹ is 2,6-disubstituted aryl,    preferably R¹ is 2,6-diisopropylphenyl, preferably R¹³ is    2-substituted aryl, preferably R¹³ is phenyl, preferably R¹ is    2,6-disubstituted aryl group and R¹³ is an aryl group lacking    substitution in the 2 and 6 positions);-   R² is a group containing 1-10 carbon atoms that is optionally joined    with R⁴ to form an aromatic ring (preferably R² & R⁴ are joined,    preferably with the joined R²R⁴ group being CHCHCH);-   R³, R³′, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each    independently selected from the group consisting of hydrogen,    hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted    hydrocarbyls, halogen, and phosphino (preferably R³ & R³′ are    hydrogen);-   J is a divalent group that forms a three-atom-length bridge between    the pyridine ring and the amido nitrogen (preferably J is selected    from the following structures);

-   n is 1 or 2;-   m is 0, 1, or 2;-   two X groups may be joined together to form a dianionic group;-   two L groups may be joined together to form a bidentate Lewis base;-   an X group may be joined to an L group to form a monoanionic    bidentate group; and adjacent groups from the following R³, R³′, R⁴,    R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² may be joined to form a ring    (preferably R⁷ & R⁸ are joined to form an aromatic ring, preferably    R⁷ & R⁸ are joined with the joined R⁷R⁸ group being CHCHCHCH,    preferably R¹⁰ & R¹¹ are joined to form a five- or six-membered    ring, preferably R¹⁰ & R¹¹ are joined with the joined R¹⁰R¹¹ group    being CH₂CH₂ or CH₂CH₂CH₂).

In a preferred embodiment, R⁴ and E form a substituted or unsubstitutedsix-membered aromatic ring.

In yet further embodiments, useful catalyst compounds include thoserepresented by the Formula (6):

-   wherein (1) M is a group 4 metal, preferably hafnium; (2) N is    nitrogen; (3) L⁷ is a group that links R⁵⁰ to Z′ by a three atom    bridge with the central of the three atoms being a group 15 or 16    element that preferably forms a dative bond to M, and is a C₅-C20    heteroaryl group containing a Lewis base functionality, especially a    divalent pyridinyl, substituted pyridinyl, quinolinyl, or    substituted quinolinyl group; (4) Z′ is a divalent linker group,    (R⁵⁶)_(p)C—C(R⁵⁷)_(q), where R⁵⁶ and R⁵⁷ are independently selected    from the group consisting of hydrogen, hydrocarbyls, substituted    hydrocarbyls, and wherein adjacent R⁵⁶ and R⁵⁷ groups may be joined    to form an aromatic or saturated, substituted or unsubstituted    hydrocarbyl ring, wherein the ring has 5, 6, 7, or 8 ring carbon    atoms and where the substituents on the ring can join to form    additional rings, and p is 1 or 2 and q is 1 or 2; (5) R⁵⁰ and R⁵³    are each, independently, ER⁵⁴R⁵⁵ with E being carbon, silicon or    germanium, and each R⁵⁴ and R⁵⁵ being independently selected from    the group consisting of hydrogen, hydrocarbyls, substituted    hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen and phosphino,    and R⁵⁴ and R⁵⁵ may be joined to form a saturated heterocyclic ring,    or a saturated substituted heterocyclic ring where substitutions on    the ring can join to form additional rings; (6) R⁵¹ and R⁵² are    independently selected from the group consisting of hydrocarbyls,    substituted hydrocarbyls, silylcarbyls and substituted silylcarbyl    groups; and (7) each X* is independently a univalent anionic ligand,    or two X*s are joined and bound to the metal atom to form a    metallocycle ring, or two X*s are joined to form a chelating ligand,    a diene ligand, or an alkylidene ligand.

In yet further embodiments, useful catalyst compounds include pyridyldiamide metal complexes represented by the following Formula (6a):

-   wherein M, X*, N, and R⁵¹, R⁵², R⁵⁴, and R⁵⁵ are as previously    defined as in Formula (6); R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶ are    independently selected from the group consisting of hydrogen,    hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen,    amino, and silyl, and wherein any one or more adjacent R⁶⁰-R⁶⁶ may    be joined to form a substituted or unsubstituted hydrocarbyl or    heterocyclic ring, wherein the ring has 5, 6, 7, or 8 ring atoms and    where substitutions on the ring can join to form additional rings.

In an embodiment of the invention, R⁶⁰ to R⁶⁶ are hydrogen.

In an embodiment of the invention, R⁶² is joined with R⁶³ to form aphenyl ring fused to the existing phenyl ring (e.g., a naphthyl group),and R⁶⁰, R⁶¹, R⁶⁴, R⁶⁵, and R⁶⁶ are independently hydrogen or an alkylgroup, preferably hydrogen.

In an embodiment of the invention, each R⁵⁴ and R⁵⁵ are independentlyhydrogen, an alkyl group or an aryl group or substituted aryl group;preferably one or both R⁵⁴ or R⁵⁵ is hydrogen, or one R⁵⁴ or R⁵⁵ ishydrogen and the other is an aryl group or substituted aryl group.Preferred, but not limiting, aryl groups for R⁵⁴ or R⁵⁵ include phenyl,2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, and naphthyl.

In an embodiment of the invention, R⁵² and R⁵¹ are independently aryl orsubstituted aryl; preferably R⁵¹ is a substituted phenyl group such as,but not limited to 2,6-diisopropylphenyl, 2,6-diethylphenyl,2,6-dimethylphenyl, mesityl, and the like, and preferably R⁵² is phenylor a substituted phenyl group such as, but not limited to 2-tolyl,2-ethylphenyl, 2-propylphenyl, 2-trifluoromethylphenyl, 2-fluorophenyl,mesityl, 2,6-diisopropylphenyl, 2,6-diethylphenyl, 2,6-dimethylphenyl,3,5-di-tert-butylphenyl, and the like.

In yet further embodiments, useful catalyst compounds include pyridyldiamide metal complexes, such as those represented by the followingFormula (6b):

-   wherein M, X*, N, R⁵¹, R⁵², R⁵⁴, R⁵⁵, R⁶¹-R⁶⁶ are as previously    defined as in Formulae (6) and (6a); each R⁷⁰-R⁷¹ are independently    selected from the group consisting of hydrogen, hydrocarbyls,    substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and    silyl, and wherein any one or more adjacent R⁷⁰-R⁷¹ may be joined to    form a substituted or unsubstituted hydrocarbyl or heterocyclic    ring, wherein the ring has 5, 6, 7, or 8 ring atoms and where    substitutions on the ring can join to form additional rings, and t    is 2 or 3 (corresponding to cyclopentyl and cyclohexyl rings,    respectively).

In an embodiment of the invention, R⁶¹-R⁶⁶ are hydrogen.

In an embodiment of the invention, each R⁷⁰ and R⁷¹ are independentlyhydrogen, and t is 2 or 3, preferably 2.

In an embodiment of the invention, each R⁵⁴ and R⁵⁵ are independentlyhydrogen, an alkyl group or an aryl group or substituted aryl group;preferably one or both R⁵⁴ or R⁵⁵ is hydrogen, or one R⁵⁴ or R⁵⁵ ishydrogen and the other is an aryl group or substituted aryl group.Preferred, but not limiting, aryl groups include phenyl and2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl and naphthyl.

In an embodiment of the invention, R⁵² and R⁵¹ are independently aryl orsubstituted aryl; preferably R⁵¹ is a substituted phenyl group such as,but not limited to 2,6-diisopropylphenyl, 2,6-diethylphenyl,2,6-dimethylphenyl, mesityl, and the like, and preferably R⁵² is phenylor a substituted phenyl group such as, but not limited to 2-tolyl,2-ethylphenyl, 2-propylphenyl, 2-trifluoromethylphenyl, 2-fluorophenyl,mesityl, 2,6-diisopropylphenyl, 2,6-diethylphenyl, 2,6-dimethylphenyl,3,5-di-tert-butylphenyl, and the like.

In an embodiment of the invention, R⁵⁴, R⁵⁵, R⁶¹-R⁶⁶, each R⁷⁰-R⁷¹ arehydrogen, R⁵² is phenyl, R⁵¹ is 2,6-diisopropylphenyl and t is 2.

Non-limiting examples of pyridyl diamide catalysts that are usefulherein are illustrated below, wherein X is methyl, benzyl, or chloro:

Additional pyridyl diamide transition metal complexes useful herein aredescribed in US 2014/0316089; WO 2012/134614; WO 2012/134615; WO2012/134613; US 2012/0071616; US 2011/0301310; and US 2010/0022726 andare incorporated by reference.

Transition metal complexes (also referred to as catalyst complexes orpre-catalyst complexes) useful herein include pyridyldiamido transitionmetal complexes represented by the Formula (A):

-   wherein:-   M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;-   E is selected from carbon, silicon, or germanium, preferably carbon;-   X is an anionic leaving group, preferably alkyl, aryl, hydride,    alkylsilane, fluoride, chloride, bromide, iodide, triflate,    carboxylate, alkylsulfonate;-   L is a neutral Lewis base, preferably ether, amine, thioether;-   R¹ and R¹³ are each independently selected from the group consisting    of hydrocarbyls, substituted hydrocarbyls, and silyl groups,    preferably aryl;-   R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are each    independently selected from the group consisting of hydrogen,    hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted    hydrocarbyls, halogen, and phosphino;-   n is 1 or 2;-   m is 0, 1, or 2;-   two X groups are optionally joined together to form a dianionic    group;-   two L groups are optionally joined together to form a bidentate    Lewis base;-   an X group may be joined to an L group to form a monoanionic    bidentate group;-   R⁷ and R⁸ are optionally joined to form a ring, preferably an    aromatic ring, a six-membered aromatic ring with the joined R⁷ and    R⁸ group being —CH═CHCH═CH—; and-   R¹⁰ and R¹¹ are optionally joined to form a ring, preferably a    five-membered ring with the joined R¹⁰ and R¹¹ group being —CH₂CH₂—,    a six-membered ring with the joined R¹⁰ and R¹¹ group being    —CH₂CH₂CH₂—.

In a preferred embodiment, R⁴, R⁵, and R⁶ are independently selectedfrom the group consisting of hydrogen, hydrocarbyls, substitutedhydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and whereinadjacent R groups (R⁴ and R⁵ and/or R⁵ and R⁶) may be joined to form asubstituted or unsubstituted hydrocarbyl or heterocyclic ring, where thering has 5, 6, 7, or 8 ring atoms and where substitutions on the ringcan join to form additional rings.

In another preferred embodiment, R⁷, R⁸, R⁹, and R¹⁰ are independentlyselected from the group consisting of hydrogen, hydrocarbyls,substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and whereinadjacent R groups (R⁷ and R⁸ and/or R⁹ and R¹⁰) may be joined to form asaturated, substituted or unsubstituted hydrocarbyl or heterocyclicring, where the ring has 5, 6, 7, or 8 ring carbon atoms and wheresubstitutions on the ring can join to form additional rings.

In still another preferred embodiment, n+m is not greater than 4.

In yet another preferred embodiment, R² and R³ are each, independently,selected from the group consisting of hydrogen, hydrocarbyls, andsubstituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, andphosphino, R² and R³ may be joined to form a saturated, substituted orunsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ringcarbon atoms and where substitutions on the ring can join to formadditional rings, or R² and R³ may be joined to form a saturatedheterocyclic ring, or a saturated substituted heterocyclic ring wheresubstitutions on the ring can join to form additional rings.

In still yet another preferred embodiment, R¹¹ and R¹² are each,independently, selected from the group consisting of hydrogen,hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino,aryloxy, halogen, and phosphino, R¹¹ and R¹² may be joined to form asaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ringcan join to form additional rings, or R¹¹ and R¹² may be joined to forma saturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings.

In a preferred embodiment, R¹ and R¹³ may be independently selected fromphenyl groups that are variously substituted with between zero to fivesubstituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino,aryl, and alkyl groups having 1 to 10 carbons, such as methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomersthereof.

Preferred R³-E-R² groups and preferred R¹²-E-R¹¹ groups include CH₂,CMe₂, SiMe₂, SiEt₂, SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂, Si(alkyl)₂,CH(aryl), CH(Ph), CH(alkyl), and CH(2-isopropylphenyl), where alkyl is aC₁ to C₄₀ alkyl group (preferably C₁ to C₂₀ alkyl, preferably one ormore of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is a C₅ toC₄₀ aryl group (preferably a C₆ to C₂₀ aryl group, preferably phenyl orsubstituted phenyl, preferably phenyl, 2-isopropylphenyl, or2-tertbutylphenyl).

In a preferred embodiment, each X may be independently selected fromhalide, alkyl, aryl, alkoxy, amido, hydrido, phenoxy, hydroxy, silyl,allyl, alkenyl, triflate, alkylsulfonate, arylsulfonate, and alkynyl.The selection of the leaving groups depends on the synthesis routeadopted for arriving at the complex and may be changed by additionalreactions to suit the later activation method in polymerization. Forexample, alkyl is preferred when using non-coordinating anions such asN,N-dimethylanilinium tetrakis(pentafluorophenyl)-borate ortris(pentafluorophenyl)borane. In another embodiment, two L groups maybe linked to form a dianionic leaving group, for example, oxalate.

In another embodiment of the invention, each L is independently selectedfrom the group consisting of ethers, thio-ethers, amines, nitriles,imines, pyridines, and phosphines, preferably ethers.

In any embodiment of the invention described herein, M is preferably aGroup 4 metal, preferably Zr or Hf.

In any embodiment of the invention described herein, each E ispreferably carbon.

In any embodiment of the invention described herein, the transitionmetal complex is represented by the Formula:

The pyridyl diamine ligands described herein are generally prepared inmultiple steps in accordance with the disclosure of U.S. Pat. No.9,290,519. An important step involves the preparation of a suitable“linker” group(s) containing both an aryl boronic acid (or acid ester)and an amine group. Examples of these include compounds of the generalFormula: 7-(boronic acid)-2,3-dihydro- 1H-inden-1-(amine), 7-(boronicacid ester)-2,3-dihydro- 1H-1-(amine), 7-(boronicacid)-1,2,3,4-tetrahydronaphthalen-1-(amine), 7-(boronic acidester)-1,2,34-tetrahydronaphthalen-1-(amine), which include variousboronic acids, boronic acid esters, and amines The linker groups may beprepared in high yield from arylhalide precursors containing aminefunctionality by first deprotonation of the amine group with 1.0 molarequivalents of n-BuLi, followed by transmetalation of an arylhalide witht-BuLi and subsequent reaction with a boron-containing reagent. Thisamine-containing linker is then coupled with a suitable pyridinecontaining species, such as 6-bromo-2-pyridinecarboxaldehyde. Thiscoupling step typically uses a metal catalyst (e.g., Pd(PPh₃)₄) in lessthan 5 mol % loading. Following this coupling step, the new derivative,which can be described as amine-linker-pyridine-aldehyde, is thenreacted with a second amine to produce the imine derivativeamine-linker-pyridine-imine in a condensation reaction. This can then bereduced to the pyridyl diamine ligand by reaction with a suitable arylanion, alkyl anion, or hydride source. This reaction is generallyperformed in etherial solvents at temperatures between −100° C. and 50°C. when aryllithium or alkyllithium reagents are employed. This reactionis generally performed in methanol at reflux when sodiumcyanoborohydride is employed.

The preparation of pyridyl diamide metal complexes from pyridyl diaminesmay be accomplished using typical protonolysis and methylationreactions. In the protonolysis reaction the pyridyl diamine is reactedwith a suitable metal reactant to produce a pyridyldiamide metalcomplex. A suitable metal reactant will feature a basic leaving groupthat will accept a proton from the pyridiyl diamine and then generallydepart and be removed from the product. Suitable metal reactantsinclude, but are not limited to, HfBn₄ (Bn═CH₂Ph), ZrBn₄, TiBn₄,ZrBn₂Cl₂(OEt₂), HtBn₂Cl₂(OEt₂)₂, Zr(NMe₂)₂Cl₂(dimethoxyethane),Hf(NMe₂)₂Cl₂(dimethoxyethane), Hf(NMe₂)₄, and Hf(NEt₂)₄. Pyridyldiamidemetal complexes that contain metal-chloride groups, such as the PDAdichloride complex, can be alkylated by reaction with an appropriateorganometallic reagent. Suitable reagents include organolithium andorganomagnesium, and Grignard reagents. The alkylations are generallyperformed in etherial or hydrocarbon solvents or solvent mixtures attemperatures typically ranging from −100° C. to 50° C.

Another route to pyridyl diamide and other complexes of interest ascatalysts involves the insertion of an unsaturated molecule into acovalent metal-carbon bond where the covalently bonded group is part ofa multidentate ligand structure, such as that described by Boussie etal. in U.S. Pat. No. 6,750,345. The unsaturated molecule will generallyhave a carbon-X double or triple bond where X is a group 14 or group 15or group 16 element. Examples of unsaturated molecules include alkenes,alkynes, imines, nitriles, ketones, aldehydes, amides, formamides,carbon dioxide, isocyanates, thioisocyanates, and carbodiimides.Examples showing the insertion reactions involving imines and carbonylsare found in U.S. Pat. No. 7,973,116 and US 2012/0071616.

In a preferred embodiment of the invention, the transition metal complexis not a metallocene. A metallocene catalyst is defined as anorganometallic compound with at least one π-bound cyclopentadienylmoiety (or substituted cyclopentadienyl moiety) and more frequently twoπ-bound cyclopentadienyl moieties or substituted cyclopentadienylmoieties.

Usefully, the single site catalyst compounds useful herein arepreferably tridentateligands bound to the transition metal (such as agroup 4 metal), preferably tridentate N,N,N ligands bound to atransition metal (such as a Zr, Hf, or Ti).

In a preferred embodiment, the catalyst complexes are represented by theFormula (Ia) or (IIa):

-   wherein:-   M is a Group 3, 4, 5, 6, 7, 8, 9, or 10 metal;-   J is a three-atom-length bridge between the quinoline and the amido    nitrogen;-   E* is selected from carbon, silicon, or germanium;-   X is an anionic leaving group;-   L is a neutral Lewis base;-   R¹ and R¹³ are independently selected from the group consisting of    hydrocarbyls, substituted hydrocarbyls, and silyl groups;-   R²* through R¹² are independently selected from the group consisting    of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy,    substituted hydrocarbyls, halogen, and phosphino;-   n is 1 or 2;-   m is 0, 1, or 2-   n+m is not greater than 4;-   any two adjacent R groups (e.g., R¹ & R², R² & R³, etc.) may be    joined to form a substituted or unsubstituted hydrocarbyl or    heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and    where substitutions on the ring can join to form additional rings;-   any two X groups may be joined together to form a dianionic group;-   any two L groups may be joined together to form a bidentate Lewis    base; and-   an X group may be joined to an L group to form a monoanionic    bidentate group.

Preferably, in Formulae Ia and IIa, M is a Group 3, 4, 5, 6, 7, 8, 9, or10 metal (preferably a group 4 metal);

-   J is group comprising a three-atom-length bridge between the    quinoline and the amido nitrogen, preferably a group containing up    to 50 non-hydrogen atoms;-   E* is carbon, silicon, or germanium;-   X is an anionic leaving group, (such as a hydrocarbyl group or a    halogen);-   L is a neutral Lewis base;-   R¹ and R¹³ are independently selected from the group consisting of    hydrocarbyls, substituted hydrocarbyls, and silyl groups;-   R^(2*), R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are    independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy,    substituted hydrocarbyl, halogen, or phosphino;-   n is 1 or 2;-   m is 0, 1, or 2, where-   n+m is not greater than 4;-   any two adjacent R groups (e.g., R¹ & R², R² & R³, etc.) may be    joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl,    substituted heterocyclic ring, or unsubstituted heterocyclic ring,    where the ring has 5, 6, 7, or 8 ring atoms and where substitutions    on the ring can join to form additional rings;-   any two X groups may be joined together to form a dianionic group;-   any two L groups may be joined together to form a bidentate Lewis    base; and-   any X group may be joined to an L group to form a monoanionic    bidentate group.

Preferably, M is a Group 4 metal, such as zirconium or hafnium.

In a preferred embodiment, J is an aromatic substituted or unsubstitutedhydrocarbyl (preferably a hydrocarbyl) having from 3 to 30 non-hydrogenatoms, preferably J is represented by the Formula:

-   where R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and E are as defined above, and any    two adjacent R groups (e.g., R⁷ & R⁸, R⁸ & R⁹, R⁹ & R¹⁰, R¹⁰ & R¹¹,    etc.) may be joined to form a substituted or unsubstituted    hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8    ring atoms (preferably 5 or 6 atoms), and said ring may be saturated    or unsaturated (such as partially unsaturated or aromatic),    preferably J is an arylalkyl (such as arylmethyl, etc.) or    dihydro-1H-indenyl, or tetrahydronaphthalenyl group.

In embodiments of the invention, J is selected from the followingstructures:

where

indicates connection to the complex.

In embodiments of the invention, E is carbon.

In embodiments of the invention, X is alkyl (such as alkyl groups having1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, and isomers thereof), aryl, hydride,alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate,amido (such as NMe₂), or alkylsulfonate.

In embodiments of the invention, L is an ether, amine or thioether.

In embodiments of the invention, R⁷ and R⁸ are joined to form asix-membered aromatic ring with the joined R⁷R⁸ group being—CH═CHCH═CH—.

In embodiments of the invention, R¹⁰ and R¹¹ are joined to form afive-membered ring with the joined R¹⁰ R¹¹ group being —CH₂CH₂—.

In embodiments of the invention, R¹⁰ and R¹¹ are joined to form asix-membered ring with the joined R¹⁰ R¹¹ group being —CH₂CH₂CH₂—.

In embodiments of the invention, R¹ and R¹³ may be independentlyselected from phenyl groups that are variously substituted with betweenzero to five substituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy,dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, and isomers thereof.

In a preferred embodiment of the invention, the quinolinyldiamidotransition metal complex represented by the Formula Ha above where: M isa Group 4 metal (preferably hafnium); E* is selected from carbon,silicon, or germanium (preferably carbon); X is an alkyl, aryl, hydride,alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate,amido, alkoxo, or alkylsulfonate; L is an ether, amine, or thioether; R¹and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups (preferablyaryl); R²*, R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² areindependently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy,substituted hydrocarbyls, halogen, and phosphino; n is 1 or 2; m is 0,1, or 2; n+m is from 1 to 4; and two X groups may be joined together toform a dianionic group; two L groups may be joined together to form abidentate Lewis base; an X group may be joined to an L group to form amonoanionic bidentate group; R⁷ and R⁸ may be joined to form a ring(preferably an aromatic ring, a six-membered aromatic ring with thejoined R⁷R⁸ group being —CH═CHCH═CH—); R¹⁰ and R¹¹ may be joined to forma ring (preferably a five-membered ring with the joined R¹⁰ R¹¹ groupbeing —CH₂CH₂—, a six-membered ring with the joined R¹⁰ R¹¹ group being—CH₂CH₂CH₂—).

In embodiments of Formula Ia and IIa, R⁴, R⁵, and R⁶ are independentlyselected from the group consisting of hydrogen, hydrocarbyls,substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl,and wherein adjacent R groups (R⁴ & R⁵ and/or R⁵ & R⁶) may be joined toform a substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstitutedheterocyclic ring or substituted heterocyclic ring, where the ring has5, 6, 7, or 8 ring atoms and where substitutions on the ring can join toform additional rings.

In embodiments of Formulae Ia and IIa, R⁷, R⁸, R⁹, and R¹⁰ areindependently selected from the group consisting of hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, andsilyl, and wherein adjacent R groups (R⁷ and R⁸, and/or R⁹ and R¹⁰) maybe joined to form a saturated, substituted hydrocarbyl, unsubstitutedhydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclicring, where the ring has 5, 6, 7, or 8 ring carbon atoms and wheresubstitutions on the ring can join to form additional rings.

In embodiments of Formula Ia or IIa, R²* and R³ are each, independently,selected from the group consisting of hydrogen, hydrocarbyls, andsubstituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, andphosphino, R²* and R³ may be joined to form a saturated, substituted orunsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ringcarbon atoms and where substitutions on the ring can join to formadditional rings, or R²* and R³ may be joined to form a saturatedheterocyclic ring, or a saturated substituted heterocyclic ring wheresubstitutions on the ring can join to form additional rings.

In embodiments of Formula Ia or IIa, R¹¹ and R¹² are each,independently, selected from the group consisting of hydrogen,hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino,aryloxy, halogen, and phosphino, R¹¹ and R¹² may be joined to form asaturated, substituted or unsubstituted hydrocarbyl ring, where the ringhas 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ringcan join to form additional rings, or R¹¹ and R¹² may be joined to forma saturated heterocyclic ring, or a saturated substituted heterocyclicring where substitutions on the ring can join to form additional rings.

In embodiments of Formula Ia or IIa, R¹ and R¹³ may be independentlyselected from phenyl groups that are variously substituted with betweenzero to five substituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy,dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, and isomers thereof.

In embodiments of Formula IIa, preferred R¹²-E*-R¹¹ groups include CH₂,CMe₂, SiMe₂, SiEt₂, SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂, Si(alkyl)₂,CH(aryl), CH(Ph), CH(alkyl), and CH(2-isopropylphenyl), where alkyl is aC₁ to C₄₀ alkyl group (preferably C₁ to C₂₀ alkyl, preferably one ormore of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is a C₅ toC₄₀ aryl group (preferably a C₆ to C₂₀ aryl group, preferably phenyl orsubstituted phenyl, preferably phenyl, 2-isopropylphenyl, or2-tertbutylphenyl).

Preferably, the R groups above and other R groups mentioned hereafter,contain from 1 to 30, preferably from 2 to 20 carbon atoms, especiallyfrom 6 to 20 carbon atoms.

Preferably, M is Ti, Zr, or Hf, and E is carbon, with Zr or Hf basedcomplexes being especially preferred.

In any embodiment of Formula IIa, described herein, E* is carbon and R¹²and R¹¹ are independently selected from phenyl groups that aresubstituted with 0, 1, 2, 3, 4, or 5 substituents selected from thegroup consisting of F, Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino,hydrocarbyl, and substituted hydrocarbyl groups with from one to tencarbons.

In any embodiment described herein of Formula IIa, R¹¹ and R¹² areindependently selected from hydrogen, methyl, ethyl, phenyl, isopropyl,isobutyl, and trimethylsilyl.

In any embodiment described herein of Formula IIa, R⁷, R⁸, R⁹, and R¹⁰are independently selected from hydrogen, methyl, ethyl, propyl,isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy,and trimethylsilyl.

In any embodiment described herein of Formula Ia or IIa, R²*, R³, R⁴,R⁵, and R⁶ are independently selected from the group consisting ofhydrogen, hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls,and halogen.

In any embodiment described herein of Formula Ia or IIa, each L isindependently selected from Et₂O, MeOtBu, Et₃N, PhNMe₂, MePh₂N,tetrahydrofuran, and dimethylsulfide.

In any embodiment described herein of Formula I or II, each X isindependently selected from methyl, benzyl, trimethylsilyl, neopentyl,ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo,dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

In any embodiment described herein of Formula Ia or IIa, R¹ is2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl,2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl,2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl,2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

In any embodiment described herein of Formula I or II, R¹³ is phenyl,2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl,2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl,3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl,4-dimethylaminophenyl, or 2-phenylphenyl.

In any embodiment described herein of Formula IIa, wherein J isdihydro-1H-indenyl and R¹ is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.

In any embodiment described herein of Formula Ia or IIa, R¹ is2,6-diisopropylphenyl and R¹³ is a hydrocarbyl group containing 1, 2, 3,4, 5, 6, or 7 carbon atoms.

For information on how to synthesize such complexes please see U.S. Ser.No. 62/357,033, filed Jun. 30, 2016.

Activators

The catalyst systems typically comprise a transition metal complex asdescribed above and an activator such as alumoxane or a non-coordinatinganion. Activation may be performed using alumoxane solution includingmethyl alumoxane, referred to as MAO, as well as modified MAO, referredto herein as MMAO, containing some higher alkyl groups to improve thesolubility. Particularly useful MAO can be purchased from Albemarle,typically in a 10 wt % solution in toluene. The catalyst system employedin the present invention may use an activator selected from alumoxanes,such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane,iso-butyl alumoxane, and the like.

When an alumoxane or modified alumoxane is used, thecomplex-to-activator molar ratio is from about 1:3000 to 10:1;alternatively 1:2000 to 10:1; alternatively 1:1000 to 10:1;alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1;alternatively 1:10 to 1:1. When the activator is an alumoxane (modifiedor unmodified), some embodiments select the maximum amount of activatorat a 5000-fold molar excess over the catalyst precursor (per metalcatalytic site). The preferred minimum activator-to-complex ratio is 1:1molar ratio.

Activation may also be performed using non-coordinating anions, referredto as NCA's, of the type described in EP 277 003 A1 and EP 277 004 A1.NCA may be added in the form of an ion pair using, for example,[DMAH]+[NCA]− in which the N,N-dimethylanilinium (DMAH) cation reactswith a basic leaving group on the transition metal complex to form atransition metal complex cation and [NCA]−. The cation in the precursormay, alternatively, be trityl. Alternatively, the transition metalcomplex may be reacted with a neutral NCA precursor, such as B(C₆F5)₃,which abstracts an anionic group from the complex to form an activatedspecies. Useful activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (i.e., [PhNMe₂H]B(C₆F₅)₄) andN,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph isphenyl, and Me is methyl.

Additionally, preferred activators useful herein include those describedin U.S. Pat. No. 7,247,687 at column 169, line 50 to column 174, line43, particularly column 172, line 24 to column 173, line 53.

In an embodiment of the invention described herein, the non-coordinatinganion activator is represented by the following Formula (1):

(Z)_(d+)(A^(d−))   (1)

wherein Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base;H is hydrogen and (L-H)+ is a Bronsted acid; A^(d−) is anon-coordinating anion having the charge d−; and d is an integer from 1to 3.

When Z is (L-H) such that the cation component is (L-H)d⁺, the cationcomponent may include Bronsted acids such as protonated Lewis basescapable of protonating a moiety, such as an alkyl or aryl, from thecatalyst precursor, resulting in a cationic transition metal species, orthe activating cation (L-H)d⁺ is a Bronsted acid, capable of donating aproton to the catalyst precursor resulting in a transition metal cation,including ammoniums, oxoniums, phosphoniums, silyliums, and mixturesthereof, or ammoniums of methylamine, aniline, dimethylamine,diethylamine, N-methylaniline, diphenylamine, trimethylamine,triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine,p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniumsfrom triethylphosphine, triphenylphosphine, and diphenylphosphine,oxoniums from ethers, such as dimethyl ether diethyl ether,tetrahydrofuran, and dioxane, sulfoniums from thioethers, such asdiethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid, it may be represented by the Formula:(Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, or a C₁to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented by theFormula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with aheteroatom, and/or a C₁ to C₄₀ hydrocarbyl. In an embodiment, thereducible Lewis acid is triphenyl carbenium.

Embodiments of the anion component Ad⁻ include those having the Formula[Mk+Qn]d⁻ wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6, or 3, 4, 5,or 6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, or boron or aluminum, and Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl radicals, said Q having up to 20 carbon atoms with theproviso that in not more than one occurrence is Q a halide, and two Qgroups may form a ring structure. Each Q may be a fluorinatedhydrocarbyl radical having 1 to 20 carbon atoms, or each Q is afluorinated aryl radical, or each Q is a pentafluoryl aryl radical.Examples of suitable Ad− components also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

In an embodiment in any of the NCA's represented by Formula 1 describedabove, the anion component Ad− is represented by the Formula[M*k*+Q*n*]d*− wherein k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5, or 6 (or1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* is independently selectedfrom hydride, bridged or unbridged dialkylamido, halogen, alkoxide,aryloxide, hydrocarbyl radicals, said Q* having up to 20 carbon atomswith the proviso that in not more than 1 occurrence is Q* a halogen.

This invention also relates to a method to polymerize olefins comprisingcontacting olefins (such as ethylene and C₄ to C₈ alpha-olefin(s)) witha catalyst complex as described above and an NCA activator representedby the Formula (2):

R_(n)M**(ArNHal)_(4−n)  (2)

where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 2also comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, or the cation is Z_(d) ⁺ as described above.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, R is selected from the group consisting of C₁to C₃₀ hydrocarbyl radicals. In an embodiment, C₁ to C₃₀ hydrocarbylradicals may be substituted with one or more C₁ to C₂₀ hydrocarbylradicals, halide, hydrocarbyl substituted organometalloid, dialkylamido,alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,arylphosphide, or other anionic substituent; fluoride; bulky alkoxides,where bulky means C₄ to C₂₀ hydrocarbyl radicals; —SRa, —NRa₂, and—PRa₂, where each Ra is independently a monovalent C₄ to C₂₀ hydrocarbylradical comprising a molecular volume greater than or equal to themolecular volume of an isopropyl substitution or a C₄ to C₂₀ hydrocarbylsubstituted organometalloid having a molecular volume greater than orequal to the molecular volume of an isopropyl substitution.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, the NCA also comprises cation comprising areducible Lewis acid represented by the Formula: (Ar₃C+), where Ar isaryl or aryl substituted with a heteroatom, and/or a C₁ to C₄₀hydrocarbyl, or the reducible Lewis acid represented by the Formula:(Ph3C⁺), where Ph is phenyl or phenyl substituted with one or moreheteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, the NCA may also comprise a cationrepresented by the Formula, (L-H)_(d) ⁺, wherein L is a neutral Lewisbase; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or(L-H)d⁺ is a Bronsted acid selected from ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. No. 7,297,653 and U.S. Pat. No. 7,799,879, which are fullyincorporated by reference herein.

In an embodiment, an activator useful herein comprises a salt of acationic oxidizing agent and a noncoordinating, compatible anionrepresented by the Formula (3):

(OX^(e+))_(d)(A^(d−))_(e)  (3)

wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; d is 1, 2, or 3; and A^(d−) is a non-coordinating anionhaving the charge of d− (as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Suitable embodiments of A^(d−) includetetrakis(pentafluorophenyl)borate.

Activators useful in catalyst systems herein include: trimethylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, and the types disclosed in U.S. Pat.No. 7,297,653, which is fully incorporated by reference herein.

Suitable activators also include:

-   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,    N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,    N,N-dimethylanilinium tetrakis    (3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium    tetrakis(perfluoronaphthyl)borate, triphenylcarbenium    tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis    (3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium    tetrakis(perfluorophenyl)borate, [Ph₃C+][B(C₆F₅)₄-],    [Me₃NH+][B(C₆F₅)₄-];    1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;    and tetrakis(pentafluorophenyl)borate,    4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In an embodiment, the activator comprises a triaryl carbonium (such astriphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In an embodiment, two NCA activators may be used in the polymerizationand the molar ratio of the first NCA activator to the second NCAactivator can be any ratio. In an embodiment, the molar ratio of thefirst NCA activator to the second NCA activator is 0.01:1 to 10,000:1,or 0.1:1 to 1000:1, or 1:1 to 100:1.

In an embodiment of the invention, the NCA activator-to-catalyst ratiois a 1:1 molar ratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to500:1 or 1:1 to 1000:1. In an embodiment, the NCA activator-to-catalystratio is 0.5:1 to 10:1, or 1:1 to 5:1.

In an embodiment, the catalyst compounds can be combined withcombinations of alumoxanes and NCA's (see for example, U.S. Pat. No.5,153,157; U.S. Pat. No. 5,453,410; EP 0 573 120 B1; WO 94/07928; and WO95/14044 which discuss the use of an alumoxane in combination with anionizing activator, all of which are incorporated by reference herein).

In a preferred embodiment of the invention, when an NCA (such as anionic or neutral stoichiometric activator) is used, thecomplex-to-activator molar ratio is typically from 1:10 to 1:1; 1:10 to10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1;1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to3:1; 1:5 to 5:1; 1:1 to 1:1.2.

Alternately, a co-activator or chain transfer agent, such as a group 1,2, or 13 organometallic species (e.g., an alkyl aluminum compound suchas tri-n-octyl aluminum), may also be used in the catalyst systemherein. The complex-to-co-activator molar ratio is from 1:100 to 100:1;1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1;1:5 to 5:1; 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.

Metal Hydrocarbenyl Transfer Agents (Aluminum Vinyl Transfer Agents)

The catalyst systems described herein further comprise a metalhydrocarbenyl transfer agent (which is any group 13 metal agent thatcontains at least one transferrable group that has an allyl chain end),preferably an aluminum vinyl-transfer agent, also referred to as anAVTA, (which is any aluminum agent that contains at least onetransferrable group that has an allyl chain end). An allyl chain end isrepresented by the Formula H₂C═CH—CH₂—. “Allylic vinyl group,” “allylchain end,” “vinyl chain end,” “vinyl termination,” “allylic vinylgroup,” “terminal vinyl group,” and “vinyl terminated” are usedinterchangeably herein and refer to an allyl chain end. An allyl chainend is not a vinylidene chain end or a vinylene chain end. The number ofallyl chain ends, vinylidene chain ends, vinylene chain ends, and otherunsaturated chain ends is determined using ¹H NMR at 120° C. usingdeuterated tetrachloroethane as the solvent on an at least 250 MHz NMRspectrometer.

Useful transferable groups containing an allyl chain end are representedby the Formula CH₂═CH—CH₂—R*, where R* represents a hydrocarbyl group ora substituted hydrocarbyl group, such as a C₁ to C₂₀ alkyl, preferablymethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, or an isomer thereof.

In the catalyst system described herein, the catalyst undergoes alkylgroup transfer with the transfer agent, which enables the formation ofpolymer chains containing one or more allyl chain ends.

Useful transferable groups containing an allyl chain end also includethose represented by the Formula CH₂═CH—CH₂—R**, where R** represents ahydrocarbeneyl group or a substituted hydrocarbeneyl group, such as a C₁to C₂₀ alkylene, preferably methylene (CH₂), ethylene [(CH₂)₂],propandiyl [(CH₂)₃], butandiyl [(CH₂)₄], pentandiyl [(CH₂)₅], hexandiyl[(CH₂)₆], heptandiyl [(CH₂)₇], octandiyl [(CH₂)₈], nonandiyl [(CH₂)₉],decandiyl [(CH₂)₁₀], undecandiyl [(CH₂₀)₁₁], dodecandiyl [(CH₂)₁₂], oran isomer thereof. Useful transferable groups are preferablynon-substituted linear hydrocarbeneyl groups. Preferably, at least oneR** is a C₄-C₂₀ hydrocarbenyl group.

The term “hydrocarbenyl” refers to a hydrocarb-di-yl divalent group,such as a C₁ to C₂₀ alkylene (i.e., methylene (CH₂), ethylene [(CH₂)₂],propandiyl [(CH₂)₃], butandiyl [(CH₂)₄], pentandiyl [(CH₂)₅], hexandiyl[(CH₂)₆], heptandiyl [(CH₂)₇], octandiyl [(CH₂)₈], nonandiyl [(CH₂)₉],decandiyl [(CH₂)₁₀], undecandiyl [(CH₂)₁₁], dodecandiyl [(CH₂)₁₂], andisomers thereof).

AVTA's are alkenylaluminum reagents capable of causing group exchangebetween the transition metal of the catalyst system (M^(TM)) and themetal of the AVTA (M^(AVTA)). The reverse reaction may also occur suchthat the polymeryl chain is transferred back to the transition metal ofthe catalyst system. This reaction scheme is illustrated below:

wherein M^(TM) is an active transition metal catalyst site and P is thepolymeryl chain, M^(AVTA) is the metal of the AVTA, and R is atransferable group containing an allyl chain end, such as a hydrocarbylgroup containing an allyl chain end, also called a hydrocarbenyl oralkenyl group.

Catalyst systems of this invention preferably have high rates of olefinpropagation and negligible or no chain termination via beta hydrideelimination, beta methyl elimination, or chain transfer to monomerrelative to the rate of chain transfer to the AVTA or other chaintransfer agent, such as an aluminum alkyl, if present. Pyridyldiamidocatalyst complexes (see U.S. Pat. No. 7,973,116; U.S. Pat. No.8,394,902; U.S. Pat. No. 8,674,040; U.S. Pat. No. 8,710,163; U.S. Pat.No. 9,102,773; US 2014/0256893; US 2014/0316089; and US 2015/0141601)activated with non-coordinating activators such as dimethyaniliniumtetrakis(perfluorophenyl)borate and/or dimethyaniliniumtetrakis(perfluoronaphthyl)borate are particularly useful in thecatalyst systems of this invention. Compound 3, described above isparticularly preferred.

In any embodiment of the invention described herein, the catalyst systemcomprises an aluminum vinyl transfer agent, which is typicallyrepresented by the Formula (I):

Al(R′)_(3−v)(R″)_(v)

where R″ is a hydrocarbenyl group containing 4 to 20 carbon atoms havingan allyl chain end, R′ is a hydrocarbyl group containing 1 to 30 carbonatoms, and v is 0.1 to 3, alternately 1 to 3, alternately 1.1 to lessthan 3, alternately v is 0.5 to 2.9, 1.1 to 2.9, alternately 1.5 to 2.7,alternately 1.5 to 2.5, alternately 1.8 to 2.2. The compoundsrepresented by the Formula Al(R′)_(3−v)(R″)_(v) are typically a neutralspecies, but anionic formulations may be envisioned, such as thoserepresented by Formula (II): [Al(R′)_(4−w)(R″)_(w)]⁻, where w is 0.1 to4, R″ is a hydrocarbenyl group containing 4 to 20 carbon atoms having anallyl chain end, and R′ is a hydrocarbyl group containing 1 to 30 carbonatoms.

In any embodiment of any formula for a metal hydrocarbenyl chaintransfer agent described herein, each R′ is independently chosen from C₁to C₃₀ hydrocarbyl groups (such as a C₁ to C₂₀ alkyl groups, preferablymethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, or an isomer thereof), and R″ is represented bythe Formula:

—(CH₂)_(n)CH═CH₂

where n is an integer from 2 to 18, preferably 6 to 18, preferably 6 to12, preferably 6. In any embodiment of the invention described herein,particularly useful AVTAs include, but are not limited to,tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum,tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum,tri(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum,diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum,diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum,diisobutyl(dec-9-en-1-yl)aluminum, diisobutyl(dodec-11-en-1-yl)aluminum,isobutyl-di(oct-7-en-1-yl)-aluminum,isobutyl-di(dec-9-en-1-yl)-aluminum,isobutyl-di(non-8-en-1-yl)-aluminum,isobutyl-di(hept-6-en-1-yl)-aluminum and the like. Mixtures of one ormore AVTAs may also be used. In some embodiments of the invention,isobutyl-di(oct-7-en-1-yl)-aluminum,isobutyl-di(dec-9-en-1-yl)-aluminum,isobutyl-di(non-8-en-1-yl)-aluminum,isobutyl-di(hept-6-en-1-yl)-aluminum are preferred.

Useful aluminum vinyl transfer agents include organoaluminum compoundreaction products between aluminum reagent (AlR^(a) ₃) and an alkyldiene. Suitable alkyl dienes include those that have two “alphaolefins,” as described above, at two termini of the carbon chain. Thealkyl diene can be a straight chain or branched alkyl chain andsubstituted or unsubstituted. Exemplary alkyl dienes include but are notlimited to, for example, 1,3-butadiene, 1,4-pentadiene, 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene,1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadecadiene,1,17-octadecadiene, 1,18-nonadecadiene, 1,19-eicosadiene,1,20-heneicosadiene, etc. Exemplary aluminum reagents includetriisobutylaluminum, diisobutylaluminumhydride,isobutylaluminumdihydride and aluminum hydride (AlH₃).

In any embodiment of the invention described herein, R″ is butenyl,pentenyl, heptenyl, octenyl, or decenyl. In some embodiments R″ ispreferably octenyl and/or decenyl.

In any embodiment of the invention described herein, R′ is methyl,ethyl, propyl, isobutyl, or butyl. In any embodiment of the inventiondescribed herein, R′ is isobutyl.

In any embodiment of the invention described herein, v is about 2, or vis 2.

In any embodiment of the invention described herein, v is about 1, or vis 1, preferably from about 1 to about 2.

In any embodiment of the invention described herein, v is an integer ora non-integer, preferably v is from 1.1 to 2.9, from about 1.5 to about2.7, e.g., from about 1.6 to about 2.4, from about 1.7 to about 2.4,from about 1.8 to about 2.2, from about 1.9 to about 2.1 and all rangesthere between.

In preferred embodiments of the invention described herein, R′ isisobutyl and each R″ is octenyl, preferably R′ is isobutyl, each R″ isoctenyl, and v is from 1.1 to 2.9, from about 1.5 to about 2.7, e.g.,from about 1.6 to about 2.4, from about 1.7 to about 2.4, from about 1.8to about 2.2, from about 1.9 to about 2.1.

In preferred embodiments of the invention described herein, R′ isisobutyl and each R″ is decenyl, preferably R′ is isobutyl, each R″ isdecenyl, and v is from 1.1 to 2.9, from about 1.5 to about 2.7, e.g.,from about 1.6 to about 2.4, from about 1.7 to about 2.4, from about 1.8to about 2.2, from about 1.9 to about 2.1.

The amount of v (the aluminum alkenyl) is described using the Formulae:(3−v)+v=3, and Al(R′)_(3−v)(R″)_(v) where R″ is a hydrocarbenyl groupcontaining 4 to 20 carbon atoms having an allyl chain end, R′ is ahydrocarbyl group containing 1 to 30 carbon atoms, and v is 0.1 to 3(preferably 1.1 to 3). This formulation represents the observed averageof organoaluminum species (as determined by ¹H NMR) present in amixture, which may include any of Al(R′)₃, Al(R′)₂(R″), Al(R′)(R″)₂, andAl(R″)₃. ¹H NMR spectroscopic studies are performed at room temperatureusing a Bruker 400 MHz NMR. Data is collected using samples prepared bydissolving 10-20 mg the compound in 1 mL of C₆D₆. Samples are thenloaded into 5 mm NMR tubes for data collection. Data is recorded using amaximum pulse width of 45°, 8 seconds between pulses and signalaveraging either 8 or 16 transients. The spectra are normalized toprotonated tetrachloroethane in the C₆D₆. The chemical shifts (δ) arereported as relative to the residual protium in the deuterated solventat 7.15 ppm.

In still another aspect, the aluminum vinyl-transfer agent has less than50 wt % dimer present, based upon the weight of the AVTA, preferablyless than 40 wt %, preferably less than 30 wt %, preferably less than 20wt %, preferably less than 15 wt %, preferably less than 10 wt %,preferably less than 5 wt %, preferably less than 2 wt %, preferablyless than 1 wt %, preferably 0 wt % dimer. Alternately dimer is presentat from 0.1 to 50 wt %, alternately 1 to 20 wt %, alternately at from 2to 10 wt %. Dimer is the dimeric product of the alkyl diene used in thepreparation of the AVTA. The dimer can be formed under certain reactionconditions, and is formed from the insertion of a molecule of diene intothe Al—R bond of the AVTA, followed by beta-hydride elimination. Forexample, if the alkyl diene used is 1,7-octadiene, the dimer is7-methylenepentadeca-1,14-diene. Similarly, if the alkyl diene is1,9-decadiene, the dimer is 9-methylenenonadeca-1,18-diene.

Useful compounds can be prepared by combining an aluminum reagent (suchas alkyl aluminum) having at least one secondary alkyl moiety (such astriisobutylaluminum) and/or at least one hydride, such as adialkylaluminum hydride, a monoalkylaluminum dihydride or aluminumtrihydride (aluminum hydride, AlH₃) with an alkyl diene and heating to atemperature that causes release of an alkylene byproduct. The use ofsolvent(s) is not required. However, non-polar solvents can be employed,such as, as hexane, pentane, toluene, benzene, xylenes, and the like, orcombinations thereof.

In an embodiment of the invention, the AVTA is free of coordinatingpolar solvents such as tetrahydrofuran and diethylether.

After the reaction is complete, solvent if, present can be removed andthe product can be used directly without further purification.

The AVTA to catalyst complex equivalence ratio can be from about 1:100to 500,000:1. More preferably, the molar ratio of AVTA to catalystcomplex is greater than 5, alternately greater than 10, alternatelygreater than 15, alternately greater than 20, alternately greater than25, alternately greater than 30.

The metal hydrocarbenyl chain transfer agent may be represented by theFormula: E[Al(R′)_(2−v)(R″)_(v)]₂ wherein E is a group 16 element (suchas O or S, preferably O); each R′, independently, is a C₁ to C₃₀hydrocarbyl group (such as a C₁ to C₂₀ alkyl group, preferably methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, or an isomer thereof); each R″, independently, is a C₄to C₂₀ hydrocarbenyl group having an allyl chain end (such as a C₁ toC₂₀ alkenyl group, preferably methenyl, ethenyl, propenyl, butenyl,pentenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, oran isomer thereof); v is from 0.01 to 3 (such as 1 or 2).

In another embodiment of the invention, the metal hydrocarbenyl chaintransfer agent is an alumoxane formed from the hydrolysis of the AVTA.Alternatively, the alumoxane can be formed from the hydrolysis of theAVTA in combination with other aluminum alkyl(s). The alumoxanecomponent is an oligomeric compound which is not well characterized, butcan be represented by the general Formula (R—Al—O)_(m) which is a cycliccompound, or may be R′(R—Al—O)_(m)-AlR′₂ which is a linear compoundwhere R′ is as defined above and at least one R′ is the same as R (asdefined above), and m is from about 4 to 25, with a range of 13 to 25being preferred. Most preferably all R′ are R. An alumoxane is generallya mixture of both the linear and cyclic compounds.

Supports

The complexes described herein may be supported (with or without anactivator and with or without a transfer agent) by any method effectiveto support other coordination catalyst systems, effectively meaning thatthe catalyst so prepared can be used for polymerizing olefin(s) in aheterogeneous process. The catalyst precursor, activator, optionaltransfer agent, co-activator if needed, suitable solvent, and supportmay be added in any order or simultaneously. Typically, the complex,activator, and optional transfer agent may be combined in solvent toform a solution. Then the support is added, and the mixture is stirredfor 1 minute to 10 hours. The total solution volume may be greater thanthe pore volume of the support, but some embodiments limit the totalsolution volume below that needed to form a gel or slurry (about 90% to400%, preferably about 100% to 200% of the pore volume).

After stirring, the residual solvent is removed under vacuum, typicallyat ambient temperature and over 10-16 hours. But greater or lesser timesand temperatures are possible.

The complex may also be supported absent the activator, and in thatcase, the activator (and co-activator if needed) is added to apolymerization process' liquid phase. Additionally, two or moredifferent complexes may be placed on the same support. Likewise, two ormore activators or an activator and co-activator may be placed on thesame support. Likewise the transfer agent may be added to thepolymerization reaction separately from the supported catalyst complexand/or activator.

Suitable solid particle supports are typically comprised of polymeric orrefractory oxide materials, each being preferably porous. Preferably,any support material that has an average particle size greater than 10μm is suitable for use in this invention. Various embodiments select aporous support material, such as for example, talc, inorganic oxides,inorganic chlorides, for example magnesium chloride and resinous supportmaterials such as polystyrene polyolefin or polymeric compounds or anyother organic support material and the like. Some embodiments selectinorganic oxide materials as the support material including

Group-2, -3, -4, -5, -13, or -14 metal or metalloid oxides. Someembodiments select the catalyst support materials to include silica,alumina, silica-alumina, and their mixtures. Other inorganic oxides mayserve either alone or in combination with the silica, alumina, orsilica-alumina. These are magnesia, titania, zirconia, and the like. Thesupport can optionally double as the activator component; however, anadditional activator may also be used.

The support material may be pre-treated by any number of methods. Forexample, inorganic oxides may be calcined, chemically treated withdehydroxylating agents such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordancewith the invention, see, for example, the descriptions in WO 95/15815and U.S. Pat. No. 5,427,991. The methods disclosed may be used with thecatalyst complexes, activators or catalyst systems of this invention toadsorb or absorb them on the polymeric supports, particularly if made upof porous particles, or may be chemically bound through functionalgroups bound to or in the polymer chains.

Useful supports typically have a surface area of from 10-700 m²/g, apore volume of 0.1-4.0 cc/g and an average particle size of 10-500 μm.Some embodiments select a surface area of 50-500 m2/g, a pore volume of0.5-3.5 cc/g, or an average particle size of 20-200 μm. Otherembodiments select a surface area of 100-400 m2/g, a pore volume of0.8-3.0 cc/g, and an average particle size of 30-100 μm. Useful supportstypically have a pore size of 10-1000 Angstroms, alternatively 50-500Angstroms, or 75-350 Angstroms.

The catalyst complexes described herein are generally deposited on thesupport at a loading level of 10-100 micromoles of complex per gram ofsolid support; alternately 20-80 micromoles of complex per gram of solidsupport; or 40-60 micromoles of complex per gram of support. However,greater or lesser values may be used provided that the total amount ofsolid complex does not exceed the support's pore volume.

Polymerization

Invention catalyst complexes are useful in polymerizing unsaturatedmonomers conventionally known to undergo coordination-catalyzedpolymerization such as solution, slurry, gas-phase, and high-pressurepolymerization. Typically, one or more of the complexes describedherein, one or more activators, one or more transfer agents (such as analuminum vinyl transfer agent) and one or more monomers are contacted toproduce polymer. The complexes may be supported and, as such, will beparticularly useful in the known, fixed-bed, moving-bed, fluid-bed,slurry, gas phase, solution, or bulk operating modes conducted insingle, series, or parallel reactors.

One or more reactors in series or in parallel may be used in the presentinvention.

The complexes, activator, transfer agent, and, when required,co-activator, may be delivered as a solution or slurry, eitherseparately to the reactor, activated in-line just prior to the reactor,or pre-activated and pumped as an activated solution or slurry to thereactor. Polymerizations are carried out in either single reactoroperation, in which monomer, comonomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers are added continuously to a single reactor or in seriesreactor operation, in which the above components are added to each oftwo or more reactors connected in series. The catalyst components can beadded to the first reactor in the series. The catalyst component mayalso be added to both reactors, with one component being added to thefirst reaction and another component to other reactors. In one preferredembodiment, the complex is activated in the reactor in the presence ofolefin and transfer agent.

In a particularly preferred embodiment, the polymerization process is acontinuous process.

Polymerization process used herein typically comprises contacting one ormore alkene monomers with the complexes, activators and transfer agentsdescribed herein. For purpose of this invention alkenes are defined toinclude multi-alkenes (such as dialkenes) and alkenes having just onedouble bond. Polymerization may be homogeneous (solution or bulkpolymerization) or heterogeneous (slurry -in a liquid diluent, or gasphase -in a gaseous diluent). In the case of heterogeneous slurry or gasphase polymerization, the complex and activator may be supported. Silicais useful as a support herein. Chain transfer agents (such as hydrogenor diethyl zinc) may be used in the practice of this invention.

The present polymerization processes may be conducted under conditionspreferably including a temperature of about 30° C. to about 200° C.,preferably from 60° C. to 195° C., preferably from 75° C. to 190° C. Theprocess may be conducted at a pressure of from 0.05 to 1500 MPa. In apreferred embodiment, the pressure is between 1.7 MPa and 30 MPa, or inanother embodiment, especially under supercritical conditions, thepressure is between 15 MPa and 1500 MPa.

If branching (such a g′_(vis) of less than 0.95) is desired in thepolymer product, then, among other things, one may increase the moles ofmetal hydrocarbenyl chain transfer agent added to the reactor relativeto the amount of polymer produced (such as grams of polymer/mols of AVTAbeing less than 500,000; 400,000 or less; 200,000 or less; 100,000 orless; 50,000 or less; 25,000 or less; 10,000 or less), and/or increasethe temperature of the polymerization reaction (such as above 80° C.),and/or increase the solids content in the polymerization reaction mass(such as 10 weight % or more, based on the weight of the componentsentering the reactor), and/or increase the residence time of thepolymerization (such as 10 minutes or more). Likewise, if a more linearpolymer is desired (such as a g′_(vis) of more than 0.95), then, amongother things, one may reduce the moles of metal hydrocarbenyl chaintransfer agent added to the reactor relative to the amount of polymerproduced (such as grams of polymer/mols of AVTA being 500,000 or more),and/or reduce the temperature of the polymerization reaction (such as80° C. or less), and/or reduce the solids content in the polymerizationreaction mass such as 10 volume % or less), and/or reduce the residencetime of the polymerization (such as 10 minutes or less). One of ordinaryskill in the art will readily appreciate that 1, 2, 3 or 4 of the aboveconditions may be varied above or below the suggested conditions aboveto obtain a desired result. For example a lower catalyst/AVTA molarratio can be used if the catalyst activity is higher.

Monomers

Monomers useful herein include olefins having from 2 to 40 carbon atoms,alternately 2 to 12 carbon atoms (preferably ethylene, propylene,butylene, pentene, hexene, heptene, octene, nonene, decene, anddodecene) and, optionally, also polyenes (such as dienes). Particularlypreferred monomers include ethylene, and mixtures of ethylene and one ormore C₄ to C₈ alpha-olefins, such as ethylene-butene, ethylene-hexene,ethylene-octene, and the like.

The catalyst systems described herein are also particularly effectivefor the polymerization of ethylene, either alone or in combination withat least one other olefinically unsaturated monomer, such as one or moreC₄ to C₂₀ α-olefin, and particularly ethylene and or a C₄ to C₈α-olefin, and more particularly ethylene and 1-hexene.

The catalyst systems described herein are also particularly effectivefor the polymerization of ethylene and C₄ to C₈ ≢-olefin, either aloneor in combination with at least one other olefinically unsaturatedmonomer, such as a C₄ to C₂₀ diene, and particularly a C₄ to C₁₂ diene.

Examples of preferred α-olefins include ethylene (C₂), propylene (C₃),butene-1 (C₄), pentene-1 (C₅), hexene-1 (C₆), heptene-1 (C₇), octene-1(C₈), nonene-1 (C₉), decene-1 (C₁₀), dodecene-1 (C₁₂),4-methylpentene-1,3-methylpentene-1,3,5,5-trimethylhexene-1, and5-ethylnonene-1. Alpha-olefins are also referred to as monomers and/orcomonomers.

Where olefins are used that give rise to short chain branching, such aspropylene, the catalyst systems may, under appropriate conditions,generate stereoregular polymers or polymers having stereoregularsequences in the polymer chains.

In a preferred embodiment, the catalyst systems described herein areused in any polymerization process described above to produce ethylenecopolymers, particularly ethylene-butene, ethylene-hexene orethylene-octene copolymers.

Scavengers

In some embodiments, when using the complexes described herein,particularly when they are immobilized on a support, the catalyst systemwill additionally comprise one or more scavenging compounds. Here, theterm scavenging compound means a compound that removes polar impuritiesfrom the reaction environment. These impurities adversely affectcatalyst activity and stability. Typically, the scavenging compound willbe an organometallic compound such as the Group-13 organometalliccompounds of U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,241,025; WO1991/09882; WO 1994/03506; WO 1993/14132; and that of WO 1995/07941.Exemplary compounds include triethyl aluminum, triethyl borane,tri-iso-butyl aluminum, methyl alumoxane, iso-butyl alumoxane,tri-n-octyl aluminum, bis(diisobutylaluminum)oxide, modifiedmethylalumoxane. (Useful modified methylalumoxane include cocatalysttype 3A (commercially available from Akzo Chemicals, Inc. under thetrade name Modified Methylalumoxane type 3A) and those described in U.S.Pat. No. 5,041,584). Those scavenging compounds having bulky or C₆-C₂₀linear hydrocarbyl substituents connected to the metal or metalloidcenter usually minimize adverse interaction with the active catalyst.Examples include triethylaluminum, but more preferably, bulky compoundssuch as tri-iso-butyl aluminum, tri-iso-prenyl aluminum, and long-chainlinear alkyl-substituted aluminum compounds, such as tri-n-hexylaluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum. Whenalumoxane is used as the activator, any excess over that needed foractivation will scavenge impurities and additional scavenging compoundsmay be unnecessary. Alumoxanes also may be added in scavengingquantities with other activators, e.g., methylalumoxane,[Me₂HNPh]⁺[B(pfp)₄]⁻ or B(pfp)₃ (perfluorophenyl=pfp=C₆F₅).

In embodiments, the transfer agent, such as the aluminum vinyl transferagent, may also function as a scavenger.

In a preferred embodiment, two or more catalyst complexes as describedherein are combined with a chain transfer agent, such as diethyl zinc ortri-n-octylaluminum, in the same reactor with monomer. Alternately, oneor more complexes are combined with another catalyst (such as ametallocene) and a chain transfer agent, such as diethyl zinc and/ortri-n-octylaluminum, in the same reactor with monomer.

Polymer Products

While the molecular weight of the polymers produced herein is influencedby reactor conditions including temperature, monomer concentration andpressure, the presence of chain terminating agents and the like, thehomopolymer and copolymer products produced by the present process mayhave an Mw of about 60,000 to about 2,000,000 g/mol, alternately ofabout 70,000 to about 600,000 g/mol, or alternately of about 100,000 toabout 500,000 g/mol, as determined by Gel Permeation Chromatography.Preferred polymers produced herein are copolymers of at least 50 mol %ethylene (preferably at least 70 mol % or more, alternatively at least80 mol % or more, alternatively at least 90 mol % or more). In apreferred embodiment, the comonomer(s) are present at preferably 50 mol% or less, alternatively 30 mol % or less, alternatively from 0.5 to 30mol %, alternatively from 1 to 25 mol %, alternatively 1 to 15 mol %,alternatively from 1 to 10 mol %. The polymers produced by the processof the invention can be used in a wide variety of products and end-useapplications.

The polymers of embodiments of the invention may have an M_(n),(number-average molecular weight) value of 60,000 g/mol or more(preferably 80,000 or more, alternatively 100,000 or more, alternatively120,000 or more, alternatively 150,000 or more, alternatively 200,000 ormore), typically from 60,000 to 1,000,000, or between from 80,000 to300,000 g/mol, or between 100,000 to 200,000. Additionally, copolymer ofembodiments of the invention will comprise a molecular weightdistribution (Mw/Mn) in the range of ≥1, or ≥1.5 to ≤4 or ≤3, preferablyfrom greater than 1 to 4, alternatively from 1.5 to 3.5, alternativelyfrom 2 to 3. Additionally, copolymer of embodiments of the invention maycomprise a molecular weight distribution Mw/Mn of 4.0 or less(preferably 3.5 or less, alternatively 3.0 or less, alternatively 2.5 orless, alternatively 2.2 or less, alternatively from 2.0 to 3.4).

Typically, polymer produced herein has an Mw of 60,000 up to 2,000,000g/mol and a g′_(vis) of 0.97 or less, or 0.95 or less, or 0.90 or less,or 0.85 or less, or 0.80 or less, or 0.70 or less, or 0.65 or less.

Preferably, the polymer produced herein is gel-free. Presence of gel canbe detected by dissolving the material in xylene at xylene's boilingtemperature (140° C.) and measuring the amount of gel present (See ASTMD 5492, except that 140° C. is used rather than 20° C.). Gel-freeproduct should be dissolved in the xylene. In one embodiment, thebranched modifier has 5 wt % or less (preferably 4 wt % or less,preferably 3 wt % or less, preferably 2 wt % or less, preferably 1 wt %or less, preferably 0 wt %) of xylene insoluble material.

In particularly useful embodiments of the invention, branchedethylene-butene, ethylene-hexene or ethylene-octene copolymers areproduced herein.

In particularly useful embodiments of the invention, the branchedethylene-butene, ethylene-hexene or ethylene-octene copolymers producedherein have a density of 0.860 to 0.980 g/cc (preferably from 0.880 to0.940 g/cc, preferably from 0.900 to 0.935 g/cc, preferably from 0.910to 0.930 g/cc).

In particularly useful embodiments of the invention, the branchedethylene-butene, ethylene-hexene or ethylene-octene copolymers producedherein have a viscosity at a frequency of 0.1 rad/sec and a temperatureof 190° C. of at least 500 Pa·s (preferably at least 5000 Pa·s,preferably from 5000 to 150,000 Pa·s, preferably from 10,000 to 100,000Pa·s).

This invention also relates to a branched polyethylene copolymercomprising at least 50 mol % ethylene (preferably at least 70 mol % ormore, preferably at least 80 mol %, preferably at least 90 mol % ormore), one or more C₄ (preferably C₆) to C₈ alpha-olefin comonomers(preferably 50 mol % or less, preferably 30 mol % or less, preferablyfrom 0.5 to 30 mol %, preferably 1 to 25 mol %, preferably 1 to 15 mol%), and a remnant of a metal hydrocarbenyl chain transfer agent(preferably at from 0.001 to 10 mol %, alternatively from 0.01 to 5 mol%, alternatively 0.01 to 2 mol %, alternatively 0.01 to 1 mol %),wherein said branched ethylene copolymer: a) has a g′_(vis), of 0.97 orless (preferably 0.95 or less, alternatively 0.92 or less, alternatively0.90 or less, alternatively, 0.88 or less, alternatively 0.85 or less,alternatively 0.80 or less, alternatively 0.70 or less, alternatively0.65 or less); b) is essentially gel free (preferably 5 wt % or less ofxylene insoluble material, alternatively 4 wt % or less, alternatively 3wt % or less, alternatively 2 wt % or less, alternatively 1 wt % orless, alternatively 0 wt %); c) has an Mw of 60,000 g/mol or more(preferably 80,000 or more, alternatively 100,000 or more, alternatively120,000 or more, alternativelyl50,000 or more); and d) has an Mw/Mn of4.0 or less (preferably 3.5 or less, alternatively 3.0 or less,alternatively 2.5 or less, alternatively 2.2 or less, alternatively from2.0 to 3.4), and e) a viscosity at 0.1 rad/sec and a temperature of 190°C. of at least 500 Pa·s (preferably from 1000 to 150,000 Pa·s,preferably from 5,000 to 125,000 Pa·s, preferably from 10,000 to 100,000Pa·s).

This invention also relates to a branched polyethylene copolymercomprising at least 50 mol % ethylene (preferably at least 70 mol % ormore, preferably at least 80 mol %, preferably at least 90 mol % ormore), one or more C₄ (preferably C₆) to C₈ alpha-olefin comonomers(preferably 50 mol % or less, preferably 30 mol % or less, preferablyfrom 0.5 to 30 mol %, preferably 1 to 25 mol %, preferably 1 to 15 mol%), and a remnant of a metal hydrocarbenyl chain transfer agent(preferably at from 0.001 to 10 mol %, alternatively from 0.01 to 5 mol%, alternatively 0.01 to 2 mol %, alternatively 0.01 to 1 mol %),wherein said branched ethylene copolymer: a) has a g′_(vis), of 0.97 orless (preferably 0.95 or less, alternatively 0.92 or less, alternatively0.90 or less, alternatively, 0.88 or less, alternatively 0.85 or less,alternatively 0.80 or less, alternatively 0.70 or less, alternatively0.65 or less); b) is essentially gel free (preferably 5 wt % or less ofxylene insoluble material, alternatively 4 wt % or less, alternatively 3wt % or less, alternatively 2 wt % or less, alternatively 1 wt % orless, alternatively 0 wt %); c) has an Mw of 60,000 g/mol or more(preferably 80,000 or more, alternatively 100,000 or more, alternatively120,000 or more, alternativelyl50,000 or more); and d) and has an Mw/Mnof 4.0 or less (preferably 3.5 or less, alternatively 3.0 or less,alternatively 2.5 or less, alternatively 2.2 or less, alternatively from2.0 to 3.4).

The branched structure of the ethylene copolymer of this invention andpolymer blends containing such branched ethylene copolymers can also beobserved by Small Amplitude Oscillatory Shear (SAOS) measurement of themolten polymer performed on a dynamic (oscillatory) rotationalrheometer. From the data generated by such a test it is possible todetermine the phase or loss angle δ, which is the inverse tangent of theratio of G″ (the loss modulus) to G′ (the storage modulus). For atypical linear polymer, the loss angle at low frequencies (or longtimes) approaches 90 degrees, because the chains can relax in the melt,adsorbing energy, and making the loss modulus much larger than thestorage modulus. As frequencies increase, more of the chains relax tooslowly to absorb energy during the oscillations, and the storage modulusgrows relative to the loss modulus. Eventually, the storage and lossmoduli become equal and the loss angle reaches 45 degrees. In contrast,a branched chain polymer relaxes very slowly, because the branches needto retract first before the chain backbone can relax along its tube inthe melt. This polymer never reaches a state where all its chains canrelax during an oscillation, and the loss angle never reaches 90 degreeseven at the lowest frequency, w, of the experiments. The loss angle isalso relatively independent of the frequency of the oscillations in theSAOS experiment; another indication that the chains can not relax onthese timescales.

As known by one of skill in the art, rheological data may be presentedby plotting the phase angle versus the absolute value of the complexshear modulus (G*) to produce a van Gurp-Palmen plot. The plot ofconventional polyethylene polymers shows monotonic behavior and anegative slope toward higher G* values. Conventional LLDPE polymerwithout long chain branches exhibit a negative slope on the vanGurp-Palmen plot. The van Gurp-Palmen plots of some embodiments of thebranched modifier polymers described in the present disclosure exhibittwo slopes—a positive slope at lower G* values and a negative slope athigher G* values.

In a plot of the phase angle δ versus the measurement frequency ω,polymers that have long chain branches exhibit a plateau in the functionof δ(ω), whereas linear polymers do not have such a plateau. Accordingto Garcia-Franco et al. (Macromolecules 2001, 34, No. 10, pp.3115-3117), the plateau in the aforementioned plot will shift to lowerphase angles δ when the amount of long chain branching occurring in thepolymer sample increases. Dividing the phase angle at which the plateauoccurs by a phase angle of 90°, one obtains the critical relaxationexponent n which can then be used to calculate a gel stiffness using theequation:

η*(ω)=SΓ(1−n)ω^(n−1)

wherein η* represents the complex viscosity (Pa·s), w represents thefrequency, S is the gel stiffness, Γ is the gamma function (see Beyer,W. H. Ed., CRC Handbook of Mathematical Sciences 5th Ed., CRC Press,Boca Rotan, 1978), and n is the critical relaxation exponent. Modifiersuseful herein preferably have a gel stiffness of more than 150 Pa·s,preferably at least 300 Pa·s, and more preferably at least 500 Pa·s. Thegel stiffness is determined at the test temperature of 190° C. Apreferred critical relaxation exponent n for the modifiers useful hereinis less than 1 and more than 0, generally, n will be between 0.1 and0.92, preferably between 0.2 and 0.85.

Small amplitude oscillatory shear data can be transformed into discreterelaxation spectra using the procedure on pages 273-275 in R. B. Bird,R. C. Armstrong, and O. Hassager, Dynamics of Polymeric Liquids, Volume1, Fluid Mechanics, 2nd Edition, John Wiley and Sons, (1987). Thestorage and loss moduli are simultaneously least squares fit with thefunctions,

G′(ω_(j))=Ση_(k)λ_(k)ω_(j) ²/(1+(η_(k)ω_(k)) ²)

G′(ω_(j))=Ση_(k)λ_(k)ω_(j)/(1+(η_(k)ω_(k))²)

at the relaxation times λ_(k)=0.01, 0.1, 1, 10, and 100 seconds. Thesums are from k=1 to k=5. The sum of the η_(k)'s is equal to the zeroshear viscosity, η₀. An indication of high levels of branched blockproducts is a high value of η₅, corresponding to the relaxation time of100 s, relative to the zero shear viscosity. The viscosity fraction ofthe 100 s relaxation time is η_(s) divided by the zero shear viscosity,η₀.

The branched ethylene copolymers used herein preferably have good shearthinning Shear thinning is characterized by the decrease of the complexviscosity with increasing shear rate. One way to quantify the shearthinning is to use a ratio of complex viscosity at a frequency of 0.01rad/s to the complex viscosity at a frequency of 100 rad/s. Preferably,the complex viscosity ratio of the modifier is 20 or more, morepreferably 50 or more, even more preferably 100 or more, when thecomplex viscosity is measured at 190° C.

Shear thinning can be also characterized using a shear thinning index.The term “shear thinning index” is determined using plots of thelogarithm (base ten) of the dynamic viscosity versus logarithm (baseten) of the frequency. The slope is the difference in the log (dynamicviscosity) at a frequency of 100 rad/s and the log (dynamic viscosity)at a frequency of 0.01 rad/s divided by 4. These plots are the typicaloutput of small amplitude oscillatory shear (SAOS) experiments. Forpurposes of this invention, the SAOS test temperature is 190° C. forethylene polymers and blends thereof. Polymer viscosity is convenientlymeasured in Pascal*seconds (Pa*s) at shear rates within a range of from0.01 to 398 rad/sec and at 190° C. under a nitrogen atmosphere using adynamic mechanical spectrometer such as the Advanced RheometricsExpansion System (ARES). Generally a low value of shear thinning indexindicates that the polymer is highly shear-thinning and that it isreadily processable in high shear processes, for example by injectionmolding. The more negative this slope, the faster the dynamic viscositydecreases as the frequency increases. Preferably, the modifier has ashear thinning index of less than −0.2. These types of modifiers areeasily processed in high shear rate fabrication methods, such asinjection molding.

The branched ethylene copolymers useful herein also preferably havecharacteristics of strain hardening in extensional viscosity. Animportant feature that can be obtained from extensional viscositymeasurements is the attribute of strain hardening in the molten state.Strain hardening is observed as a sudden, abrupt upswing of theextensional viscosity in the transient extensional viscosity vs. timeplot. This abrupt upswing, away from the behavior of a linearviscoelastic material, was reported in the 1960s for LDPE (reference: J.Meissner, Rheol. Acta., Vol. 8, 78, 1969) and was attributed to thepresence of long branches in the polymer. The strain-hardening ratio(SHR) is defined as the ratio of the maximum transient extensionalviscosity over three times the value of the transient zero-shear-rateviscosity at the same strain rate. Strain hardening is present in thematerial when the ratio is greater than 1. In one embodiment, thebranched modifiers show strain-hardening in extensional flow. Preferablythe strain-hardening ratio is 2 or greater, preferably 5 or greater,more preferably 10 or greater, and even more preferably 15 or more, whenextensional viscosity is measured at a strain rate of 1 sec⁻¹ and at atemperature of 150° C.

The branched ethylene copolymers also generally exhibits melt strengthvalues greater than that of conventional linear or long chain branchedpolyethylene of similar melt index. As used herein, “melt strength”refers to the force required to draw a molten polymer extrudate at arate of 12 mm/s² at an extrusion temperature of 190° C. until breakageof the extrudate whereby the force is applied by take up rollers. In oneembodiment, the melt strength of the branched modifier polymer is atleast 20% higher than that of a linear polyethylene with the samedensity and MI.

In a preferred embodiment, the branched ethylene copolymers have astrain hardening ratio of 5 or more, preferably 10 or more, preferably20 or more, preferably 30 or more, preferably 40 or more, preferably 50or more; and/or an Mw of 50,000 g/mol or more, preferably from 50,000 to2,000,000 g/mol, alternately from 100,000 to 1,000,000 g/mol,alternately from 150,000 to 750,000 g/mol.

End Uses

The polymers of this invention may be used alone or may be blendedand/or coextruded with any other polymer. Non-limiting examples of otherpolymers include linear low density polyethylenes, elastomers,plastomers, high pressure low density polyethylene, high densitypolyethylenes, isotactic polypropylene, ethylene propylene copolymersand the like.

Preferred ethylene polymers and copolymers that are useful as polymerblend components include those sold by ExxonMobil Chemical Company inHouston Tex. including those sold as ExxonMobil HDPE, ExxonMobil LLDPE,and ExxonMobil LDPE; and those sold under the ENABLE™, EXACT™, EXCEED™,ESCORENE™, EXXCO™, ESCOR™, PAXON™, and OPTEMA™ tradenames.

In another embodiment, the ethylene polymers and copolymers that areuseful as polymer blend components comprises one or more mPEs describedin US 2007/0260016 and U.S. Pat. No. 6,476,171, e.g., copolymers of anethylene and at least one alpha olefin having at least 5 carbon atomsobtainable by a continuous gas phase polymerization using supportedcatalyst of an activated molecularly discrete catalyst in thesubstantial absence of an aluminum alkyl based scavenger (e.g.,triethylaluminum, trimethylaluminum, tri-isobutyl aluminum,tri-n-hexylaluminum, and the like), which polymer has a Melt Index offrom 0.1 to 15 (ASTM D 1238, condition E); a CDBI of at least 70%, adensity of from 0.910 to 0.930 g/cc; a Haze (ASTM D1003) value of lessthan 20; a Melt Index ratio (121/12, ASTMD 1238) of from 35 to 80; anaveraged Modulus (M) (as defined in U.S. Pat. No. 6,255,426) of from20,000 to 60,000 psi (13790 to 41369 N/cm²); and a relation between Mand the Dart Impact Strength (26 inch, ASTM D 1709) in g/mil (DIS)complying with the Formula:

DIS≥0.8×[100_(+e) ^((11.71−0.000268×M+2.183×10) ⁻⁹ ^(×M) ² ⁾],

where “e” represents 2.1783, the base Napierian logarithm, M is theaveraged Modulus in psi and DIS is the 26 inch (66 cm) dart impactstrength. (See U.S. Pat. No. 6,255,426 for further description of suchethylene polymers.)

In another embodiment, the ethylene polymers and copolymers that areuseful as polymer blend components comprises a Ziegler-Nattapolyethylene, e.g., CDBI less than 50, preferably having a density of0.910 to 0.950 g/cm³ (preferably 0.915 to 0.940 g/cm³, preferably 0.918to 0.925 g/cm³).

In another embodiment, the ethylene polymers and copolymers that areuseful as polymer blend components comprises olefin block copolymers asdescribed in EP 1 716 190.

In another embodiment, the ethylene polymers and copolymers that areuseful as polymer blend components is produced using chrome basedcatalysts, such as, for example, in U.S. Pat. No. 7,491,776 includingthat fluorocarbon does not have to be used in the production. Commercialexamples of polymers produced by chromium include the Paxon™ grades ofpolyethylene produced by ExxonMobil Chemical Company, Houston Tex.

In another embodiment, the ethylene polymers and copolymers that areuseful as polymer blend components comprises ethylene and an optionalcomonomer of propylene, butene, pentene, hexene, octene nonene ordecene, and said polymer has a density of more than 0.86 to less than0.910 g/cm³, an Mw of 20,000 g/mol or more (preferably 50,000 g/mol ormore) and a CDBI of 90% or more.

In another embodiment, the ethylene polymers and copolymers that areuseful as polymer blend components comprises a substantially linear andlinear ethylene polymers (SLEPs). Substantially linear ethylene polymersand linear ethylene polymers and their method of preparation are fullydescribed in U.S. Pat. Nos. 5,272,236; 5,278,272; 3,645,992; 4,937,299;4,701,432; 4,937,301; 4,935,397; 5,055,438; EP 129,368; EP 260,999; andWO 90/07526, which are fully incorporated herein by reference. As usedherein, “a linear or substantially linear ethylene polymer” means ahomopolymer of ethylene or a copolymer of ethylene and one or morealpha-olefin comonomers having a linear backbone (i.e., no crosslinking), a specific and limited amount of long-chain branching or nolong-chain branching, a narrow molecular weight distribution, a narrowcomposition distribution (e.g., for alpha-olefin copolymers), or acombination thereof. More explanation of such polymers is discussed inU.S. Pat. No. 6,403,692, which is incorporated herein by reference forall purposes.

Articles made using polymers produced herein and or blends thereof mayinclude, for example, molded articles (such as containers and bottles,e.g., household containers, industrial chemical containers, personalcare bottles, medical containers, fuel tanks, and storageware, toys,sheets, pipes, tubing) films, non-wovens, and the like. It should beappreciated that the list of applications above is merely exemplary, andis not intended to be limiting.

In particular, polymers produced by the process of the invention andblends thereof are useful in such forming operations as film, sheet, andfiber extrusion and co-extrusion as well as blow molding, injectionmolding, roto-molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing film or oriented films.

EXPERIMENTAL

Aluminum Vinyl Transfer Agent

All manipulations were performed under an inert atmosphere using glovebox techniques unless otherwise stated. Benzene-d₆ (Cambridge Isotopes)(Sigma Aldrich) was degassed and dried over 3 Å molecular sieves priorto use. CDCl₃ (Deutero GmbH) was used as received.

Diisobutylaluminum hydride (DIBAL-H) was purchased from Akzo NobelSurface Chemistry LLC and used as received. 1,7-octadiene and1,9-decadiene were purchased from Sigma Aldrich and purified by thefollowing procedure prior to use. The diene was purged under nitrogenfor 30 minutes and then this was stored over 3 Å molecular sieves forovernight. Further this was stirred with NaK (sodium-potassium alloy)for overnight and then filtered through basic alumina column prior touse.

EXAMPLE 1 Preparation of diisobutyl(oct-7-en-1-yl)aluminum,^(i)Bu₂Al(Oct=) (AVTA1)

A neat 1,7-octadiene (16.53 g, 150 mmol) was added drop wise todiisobutylaluminium hydride (3.56 g, 25 mmol) at room temperature over aperiod of 5 minutes. The reaction mixture was either stirred at 45° C.for overnight. The excess 1,7-octadiene from the reaction mixture wasremoved under the flow of dry nitrogen at room temperature. The residual1,7-octadiene was then removed in vacuo for 30 minutes to obtain acolorless viscous oil of diisobutyl(oct-7-en-1-yl) aluminum,iBu2Al(Oct=) (5.093 g, 90%). The product formation was confirmed by ¹HNMR spectroscopy and based on the relative integration the molecularformula was assigned as (C₄H₉)_(2.03)Al(C₈H₁₅)_(0.97). ¹H NMR (400 MHz,benzene-d₆): δ=5.78 (m, 1H, ═CH), 5.01 (m, 2H, ═CH₂), 1.95 (m, 4H,—CH₂), 1.54 (m, 2H, ^(i)Bu-CH), 1.34 (m, 6H, —CH₂), 1.04 (d, 12H,¹Bu-CH₃), 0.49 (t, 2H, Al—CH₂), 0.27 (d, 4H, ^(i)Bu-CH₂) ppm.

EXAMPLE 2 Preparation of Isobutyldi(oct-7-en-1-yl)aluminum,^(i)BuAl(Oct=)₂ (AVTA2) Example 2A:

A neat 1,7-octadiene (22.91 g, 207.9 mmol) was added drop wise todiisobutylaluminum hydride (2.61 g, 18.4 mmol) at room temperature over5 minutes. The resulting mixture was stirred under reflux at 110° C. for60 minutes and then continuously stirring at 70° C. for overnight. Theexcess 1,7-octadiene from the reaction mixture was removed under theflow of dry nitrogen at room temperature. The residual 1,7-octadiene wasthen removed in vacuum to obtain a colorless viscous oil ofisobutyldi(oct-7-en-1-yl)aluminum, iBuAl(Oct=)₂ (5.53 g, 97%). Theproduct formation was confirmed by ¹H NMR and based on the relativeintegration the molecular formula of was assigned as(C₄H₉)_(0.95)Al(C₈H₁₅)_(2.05). ¹H NMR (400 MHz, benzene-d6): δ=5.81 (m,2H, ═CH), 5.05 (m, 4H, ═CH₂), 2.03 (m, 8H, —CH₂), 1.59 (m, 1H,^(i)Bu-CH), 1.38 (m, 12H, —CH₂), 1.09 (d, 6H, ^(i)Bu-CH₃), 0.51 (t, 4H,Al—CH₂), 0.31 (d, 2H, ^(i)Bu-CH₂) ppm.

Example 2B:

A neat 1,7-octadiene (22.91 g, 207.9 mmol) was added drop wise todiisobutylaluminium hydride (2.6 g, 18.4 mmol) at room temperature over5 minutes. The resulting mixture was stirred under reflux at 110° C. for60 minutes and then continuously stirring at 70° C. for overnight. Theexcess 1,7-octadiene from the reaction mixture was removed under theflow of dry nitrogen at room temperature. The residual 1,7-octadiene wasthen removed in vacuum to obtain a colorless viscous oil ofisobutyldi(oct-7-en-1-yl)aluminum, iBuAl(Oct=)₂ (5.306 g, 94%). Theproduct formation was confirmed by ¹H NMR and based on the relativeintegration the molecular formula of was assigned as(C₄H₉)_(0.98)Al(C₈H₁₅)_(2.02).

For AVTA2, 3.427 g of Example 2A and 4.792 g of Example 2B were blendedtogether to make AVTA2.

EXAMPLE 3 Preparation of Isobutyldi(dec-9-en-1-yl)aluminum,^(i)BuAl(Dec=)₂ (AVTA3)

1,9-Decadiene (500 mL, 2.71 mol) was loaded into a round-bottomed flask.Diisobutylaluminum hydride (30.2 mL, 0.170 mol) was added dropwise over15 minutes. The mixture was then placed in a metal block maintained at110° C. After 30 minutes the solution had stabilized at a temperature of104° C. The mixture was kept at this temperature for an additional 135minutes at which time H-NMR spectroscopic data indicated that thereaction had progressed to the desired amount. The mixture was cooled toambient temperature. The excess 1,9-decadiene was removed by vacuumdistillation at 44° C./120 mTorr over a 2.5 hours. The product wasfurther distilled at 50° C./120 mTorr for an additional hour to ensurecomplete removal of all 1,9-decadiene. The isolated product was a clearcolorless oil. The yield was 70.9 g. H-NMR spectroscopic data indicatedan average formula of Al(iBu)_(0.9)(decenyl)_(2.1), with a small amount(ca. 0.2 molar equivalents) of vinylidene containing byproduct, that maybe formed by the insertion of 1,9-decadiene into an Al-octenyl bondfollowed by beta hydride elimination.

Activator and Catalyst Complexes

Complex 1 was prepared as described in U.S. Pat. No. 9,290,519. Theactivator used was dimethylanilinium tetrakis(pentafluorophenyl)borane(available from Albemarle Corp. or Boulder Scientific).

Polymerization

Polymerizations were carried out in a continuous stirred tank reactorsystem. A 1-liter Autoclave reactor was equipped with a stirrer, apressure controller, and a water cooling/steam heating element with atemperature controller. The reactor was operated in liquid fillcondition at a reactor pressure in excess of the bubbling point pressureof the reactant mixture, keeping the reactants in liquid phase.Isohexane was pumped into the reactors by Pulsa feed pumps and hexenewas fed under N₂ head pressure in a holding tank. All flow rates ofliquid were controlled using Coriolis mass flow controller (Quantimseries from Brooks). Ethylene flowed as a gas under its own pressurethrough a Brooks flow controller. Ethylene and hexene feeds werecombined into one stream and then mixed with a pre-chilled isohexanestream that had been cooled to at least 0° C. The mixture was then fedto the reactor through a single line. Solutions of TNOA or AVTA wasadded to the combined solvent and monomer stream just before theyentered the reactor. Catalyst solution was fed to the reactor using anISCO syringe pump through a separated line.

Isohexane (used as solvent), and monomers (e.g., ethylene and hexene)were purified over beds of alumina and molecular sieves. Toluene forpreparing catalyst solutions was purified by the same technique.

The catalyst solution was prepared by activating the pre-catalyst,complex A (80 mg), with N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate at a molar ratio of about 1:1 in 900ml of toluene. Solution of tri-n-octyl aluminum (TNOA) (25 wt % inhexane, Sigma Aldrich) was further diluted in isohexane at aconcentration of 1.815×10⁻² mol/liter. AVTA was diluted in toluene atthe concentration of 1.79×10⁻² mol/liter.

The polymer produced in the reactor exited through a back pressurecontrol valve that reduced the pressure to atmospheric. This caused theunconverted monomers in the solution to flash into a vapor phase whichwas vented from the top of a vapor liquid separator. The liquid phase,comprising mainly polymer and solvent, was collected for polymerrecovery. The collected samples were first air-dried in a hood toevaporate most of the solvent, and then dried in a vacuum oven at atemperature of about 90° C. for about 12 hours. The vacuum oven driedsamples were weighed to obtain yields.

The detailed polymerization process conditions and some characteristicproperties are listed in Table 1. The catalyst feed rates may also beadjusted according to the level of impurities in the system to reach thetargeted conversions listed. All the reactions were carried out at apressure of about 2.4 MPa/g unless otherwise mentioned. For comparison,

TNOA solution was used in Examples 1 and 4 as a comparison.

TABLE 1 Ethylene Hexene copolymerizations Example # C1 1 2 C2 3 4Polymerization 120 120 120 130 130 130 temperature (° C.) Ethylene feedrate 5.66 5.66 5.66 5.66 5.66 5.66 (g/min) 1-hexene feed rate 3 3 3 3 33 (g/min) Catalyst feed rate 1.9 × 10⁻⁰⁷ 1.9 × 10⁻⁰⁷ 1.9 × 10⁻⁰⁷ 2.5 ×10⁻⁰⁷ 2.5 × 10⁻⁰⁷ 2.5 × 10⁻⁰⁷ rate (mol/min) Scavenger/AVTA TNOA AVTA1AVTA1 TNOA AVTA2 AVTA2 Scavenger/AVTA 2.7 × 10⁻⁵  0.00011 7.2 × 10⁻⁵ 7.4 × 10⁻⁶  0.022 0.033 feed rate (mol/min) Isohexane feed rate 55.255.2 55.2 56.7 56.7 56.7 (g/min) Yield (gram/min) 4.8 4.5 5.1 6.5 5.04.8 Conversion 55.9% 51.4% 58.4% 74.9% 58.1% 55.0% Tc (° C.) 79.9 85.179.3 59.6 79.5 85.0 Tm (° C.) 98.0 103.2 96.9 79.6 99.0 101.2 Heat offusion (J/g) 99.1 108.5 99.4 81.1 104.9 108.3 Hexene (wt %) 12.5 11.613.7 18.6 13.2 12.0 Mn_DRI (g/mol) 62,365 25,711 40,256 94,103 53,10632,902 Mw_DRI (g/mol) 127,327 63,722 104,919 231,740 143,768 102,125Mz_DRI (g/mol) 221,133 148,739 251,764 399,961 369,377 319,981 Mn_LS(g/mol) 71,936 29,308 46,791 110,753 59,673 37,138 Mw_LS (g/mol) 133,84164,602 107,827 221,383 143,036 102,994 Mz_LS (g/mol) 235,532 160,659256,977 351,010 359,794 358,926 g′_(vis) 1.005 0.95 0.959 1.005 0.9090.877 Mw/Mn 1.86 2.20 2.30 2.00 2.40 2.77 Mz/Mn 3.27 5.48 5.49 3.17 6.039.66 MI (I₂) 0.58 2.82 0.19 0.113 I₂₁ 12.40 108.60 13.40 1.98 5.21 16.17MIR 21.38 38.51 70.53 143.07

Test Methods

Unsaturated Chain Ends: The number of vinyl chain ends, vinylidene chainends and vinylene chain ends is determined using ¹H NMR using1,1,2,2-tetrachloroethane-d₂ as the solvent on an at least 400 MHz NMRspectrometer. Proton NMR data is collected at 120° C. in a 5 mm probeusing a Varian spectrometer with a ¹H frequency of at least 400 MHz.Data was recorded using a maximum pulse width of 45°, 5 seconds betweenpulses and signal averaging 120 transients. Spectral signals wereintegrated and the number of unsaturation types per 1000 carbons wascalculated by multiplying the different groups by 1000 and dividing theresult by the total number of carbons.

The chain end unsaturations are measured as follows. The vinylresonances of interest are between from 5.0 to 5.1 ppm (VRA), thevinylidene resonances between from 4.65 to 4.85 ppm (VDRA), the vinyleneresonances from 5.31 to 5.55 ppm (VYRA), the trisubstituted unsaturatedspecies from 5.11 to 5.30 ppm (TSRA) and the aliphatic region ofinterest between from 0 to 2.1 ppm (IA).

The number of vinyl groups/1000 Carbons is determined from the Formula:(VRA *500)/((IA+VRA+VYRA+VDRA)/2)+TSRA). Likewise, the number ofvinylidene groups/1000 Carbons is determined from the Formula:(VDRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA), the number of vinylenegroups/1000 Carbons from the Formula(VYRA*500)/((IA+VRA+VYRA+VDRA)/2)25+TSRA) and the number oftrisubstituted groups from the Formula(TSRA*1000)/((IA+VRA+VYRA+VDRA)/2) +TSRA). VRA, VDRA, VYRA, TSRA and IAare the integrated normalized signal intensities in the chemical shiftregions defined above. Vinyl chain ends are reported as a molarpercentage of the total number of moles of unsaturated polymerend-groups (that is, the sum of vinyl chain ends, vinylidene chain ends,vinylene chain ends, and trisubstituted olefinic chain ends).

Molecular Weight: Unless otherwise indicated, molecular weight(weight-average molecular weight, M_(w), number-average molecularweight, M_(n), and molecular weight distribution, M_(w)/M_(n), or MWD,and branching index (g′vis)) are determined via GPC 3D using a HighTemperature Size Exclusion Chromatograph (either from Waters Corporationor Polymer Laboratories), equipped with a differential refractive indexdetector (DRI), an online light scattering (LS) detector, and aviscometer. Experimental details not described below, including how thedetectors are calibrated, are described in: T. Sun, P. Brant, R. R.Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001).

Three Polymer Laboratories PLgel 10 mm Mixed-B columns are used. Thenominal flow rate was 0.5 cm³/min, and the nominal injection volume is300 μL. The various transfer lines, columns and differentialrefractometer (the DRI detector) are contained in an oven maintained at135° C. Solvent for the SEC experiment is prepared by dissolving 6 gramsof butylated hydroxy toluene as an antioxidant in 4 liters of Aldrichreagent grade 1, 2, 4 trichlorobenzene (TCB). The TCB mixture is thenfiltered through a 0.7 pm glass pre-filter and subsequently through a0.1 μm Teflon filter. The TCB is then degassed with an online degasserbefore entering the SEC. Polymer solutions are prepared by placing drypolymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous agitation for about 2hours. All quantities are measured gravimetrically. The TCB densitiesused to express the polymer concentration in mass/volume units are 1.463g/ml at room temperature and 1.324 g/ml at 135° C. The injectionconcentration ranges from 1.0 to 2.0 mg/ml, with lower concentrationsbeing used for higher molecular weight samples. Prior to running eachsample the DRI detector and the injector are purged. Flow rate in theapparatus is then increased to 0.5 ml/minute, and the DRI is allowed tostabilize for 8-9 hours before injecting the first sample. The LS laseris turned on 1 to 1.5 hours before running samples.

The concentration, c, at each point in the chromatogram is calculatedfrom the baseline-subtracted DRI signal, I_(DRI), using the followingequation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the same as described below for the light scattering (LS)analysis. Units on parameters throughout this description of the SECmethod are such that concentration is expressed in g/cm³, molecularweight is expressed in g/mole, and intrinsic viscosity is expressed indL/g.

The light scattering detector used is a Wyatt Technology HighTemperature mini-DAWN. The polymer molecular weight, M, at each point inthe chromatogram is determined by analyzing the LS output using the Zimmmodel for static light scattering (M. B. Huglin, LIGHT SCATTERING FROMPOLYMER SOLUTIONS, Academic Press, 1971):

$\frac{K_{o}c}{\Delta \; {R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2\; A_{2}{c.}}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient [for purposes of thisinvention and the claims thereto, A₂=0.0006 for propylene polymers and0.001 otherwise], P(θ) is the form factor for a monodisperse random coil(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971), and K_(o) is the optical constant for the system:

$K_{o} = \frac{4\; \pi^{2}{n^{2}\left( {{dn}/{dc}} \right)}^{2}}{\lambda^{4}N_{A}}$

in which N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 135°C. and λ=690 nm. For purposes of this invention and the claims thereto(dn/dc) =0.104 for propylene polymers and 0.1 otherwise.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, at each point in the chromatogram is calculatedfrom the following equation:

η_(s) =c[η]+0.3(c[η])²

where c is concentration and is determined from the DRI output.

The branching index, g′ (also referred to as g′_(vis)), is calculatedusing the output of the SEC-DRI-LS-VIS method as follows. The averageintrinsic viscosity, [η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum\; {c_{i}\lbrack\eta\rbrack}_{i}}{\sum\; c_{i}}$

where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′_(vis) is defined as:

$g^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

where, for purpose of this invention and claims thereto, α=0.695 forethylene, propylene, and butene polymers; and k=0.000579 for ethylenepolymers, k=0.000262 for propylene polymers, and k=0.000181 for butenepolymers. M_(v) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis.

Comonomer Content (such as for butene, hexene and octene) was determinedvia FTIR measurements according to ASTM D3900 (calibrated versus ¹³CNMR). A thin homogeneous film of polymer, pressed at a temperature ofabout 150° C., was mounted on a Perkin Elmer Spectrum 2000 infraredspectrophotometer. The weight percent of copolymer is determined viameasurement of the methyl deformation band at about 1375 cm⁻¹. The peakheight of this band is normalized by the combination and overtone bandat about 4321 cm⁻¹, which corrects for path length differences.

Melt Index (MI, also referred to as I₂) is measured according to ASTMD1238 at 190° C., under a load of 2.16 kg unless otherwise noted. Theunits for MI are g/10 min or dg/min.

High Load Melt Index (HLMI, also referred to as I₂₁) is the melt flowrate measured according to ASTM D-1238 at 190° C., under a load of 21.6kg. The units for HLMI are g/10 min or dg/min.

Melt Index Ratio (MIR) is the ratio of the high load melt index to themelt index, or I₂₁/I₂.

Density is measured by density-gradient column, as described in ASTMD1505, on a compression-molded specimen that has been slowly cooled toroom temperature (i.e., over a period of 10 minutes or more) and allowedto age for a sufficient time that the density is constant within +/−0.001 g/cm³. The units for density are g/cm³.

Peak melting point, Tm, (also referred to as melting point), peakcrystallization temperature, Tc, (also referred to as crystallizationtemperature), glass transition temperature (Tg), heat of fusion (ΔHf orHf), and percent crystallinity were determined using the following DSCprocedure according to ASTM D3418-03. Differential scanning calorimetric(DSC) data were obtained using a TA Instruments model Q200 machine.Samples weighing approximately 5-10 mg were sealed in an aluminumhermetic sample pan. The DSC data were recorded by first graduallyheating the sample to 200° C. at a rate of 10° C./minute. The sample waskept at 200° C. for 2 minutes, then cooled to −90° C. at a rate of 10°C./minute, followed by an isothermal for 2 minutes and heating to 200°C. at 10° C./minute. Both the first and second cycle thermal events wererecorded. Areas under the endothermic peaks were measured and used todetermine the heat of fusion and the percent of crystallinity. Thepercent crystallinity is calculated using the formula, [area under themelting peak (Joules/gram)/B (Joules/gram)]*100, where B is the heat offusion for the 100% crystalline homopolymer of the major monomercomponent. These values for B are to be obtained from the PolymerHandbook, Fourth Edition, published by John Wiley and Sons, New York1999, provided; however, that a value of 189 J/g (B) is used as the heatof fusion for 100% crystalline polypropylene, a value of 290 J/g is usedfor the heat of fusion for 100% crystalline polyethylene. The meltingand crystallization temperatures reported here were obtained during thesecond heating/cooling cycle unless otherwise noted.

For polymers displaying multiple endothermic and exothermic peaks, allthe peak crystallization temperatures and peak melting temperatures werereported. The heat of fusion for each endothermic peak was calculatedindividually. The percent crystallinity is calculated using the sum ofheat of fusions from all endothermic peaks. Some of polymer blendsproduced show a secondary melting/cooling peak overlapping with theprincipal peak, which peaks are considered together as a singlemelting/cooling peak. The highest of these peaks is considered the peakmelting temperature/crystallization point. For the amorphous polymers,having comparatively low levels of crystallinity, the meltingtemperature is typically measured and reported during the first heatingcycle. Prior to the DSC measurement, the sample was aged (typically byholding it at ambient temperature for a period of 2 days) or annealed tomaximize the level of crystallinity.

Gauge, reported in mils, was measured using a Measuretech Series 200instrument. The instrument measures film thickness using a capacitancegauge. For each film sample, ten film thickness data points weremeasured per inch of film as the film was passed through the gauge in atransverse direction. From these measurements, an average gaugemeasurement was determined and reported. Coefficient of variation (GaugeCOV) is used to measure the variation of film thickness in thetransverse direction. The Gauge COV is defined as a ratio of thestandard deviation to the mean of film thickness.

Elmendorf Tear, reported in grams (g) or grams per mil (g/mil), wasmeasured as specified by ASTM D-1922.

Tensile Strength at Yield, Tensile Strength at Break, Ultimate TensileStrength and Tensile Strength at 50%, 100%, and/or 200% Elongation weremeasured as specified by ASTM D-882.

Tensile Peak Load was measured as specified by ASTM D-882.

Tensile Energy, reported in inch-pounds (in-lb), was measured asspecified by ASTM D-882.

Elongation at Yield and Elongation at Break, reported as a percentage(%), were measured as specified by ASTM D-882.

1% Secant Modulus (M), reported in pounds per square inch (lb/in² orpsi), was measured as specified by ASTM D-882.

Haze, reported as a percentage (%), was measured as specified by ASTMD-1003.

Gloss, a dimensionless number, was measured as specified by ASTM D-2457at 45 degrees.

Dart Drop Impact or Dart Drop Impact Strength (DIS), reported in grams(g) and/or grams per mil (g/mil), was measured as specified by ASTMD-1709, method A, unless otherwise specified.

Peak Puncture Force, reported in pounds (lb) and/or pounds per mil(lb/mil), was determined according to ASTM D-3763.

Puncture Break Energy, reported in inch-pounds (in-lb) and/orinch-pounds per mil (in-lb/mil), was determined according to ASTM D-3763

“Melt strength” is defined as the force required to draw a moltenpolymer extrudate at a rate of 12 mm/s² and at an extrusion temperatureof 190° C. until breakage of the extrudate whereby the force is appliedby take up rollers. The polymer is extruded at a velocity of 0.33 mm/sthrough an annular die of 2 mm diameter and 30 mm length. Melt strengthvalues reported herein are determined using a Gottfert Rheotens testerand are reported in centi-Newtons (cN). Additional experimentalparameters for determining the melt strength are listed in the tablebelow. For the measurements of melt strength, the resins were stabilizedwith 500 ppm of Irganox 1076 and 1500 ppm of Irgafos168.

Melt Strength test parameters Acceleration 12 mm/s² Temperature 190° C.Piston diameter 12 mm Piston speed 0.178 mm/s Die diameter 2 mm Dielength 30 mm Shear rate at the die 40.05 s⁻¹ Strand length 100.0 mm Vo(velocity at die exit) 10.0 mm/s

Dynamic shear melt rheological data was measured with an AdvancedRheometrics Expansion System (ARES) using parallel plates (diameter=25mm) in a dynamic mode under nitrogen atmosphere. For all experiments,the rheometer was thermally stable at 190° C. for at least 30 minutesbefore inserting compression-molded sample of resin onto the parallelplates. To determine the samples viscoelastic behavior, frequency sweepsin the range from 0.01 to 385 rad/s were carried out at a temperature of190° C. under constant strain. Depending on the molecular weight andtemperature, strains of 10% and 15% were used and linearity of theresponse was verified. A nitrogen stream was circulated through thesample oven to minimize chain extension or cross-linking during theexperiments. All the samples were compression molded at 190° C. and nostabilizers were added. A sinusoidal shear strain is applied to thematerial if the strain amplitude is sufficiently small the materialbehaves linearly. It can be shown that the resulting steady-state stresswill also oscillate sinusoidally at the same frequency but will beshifted by a phase angle δ with respect to the strain wave. The stressleads the strain by δ. For purely elastic materials δ=0° (stress is inphase with strain) and for purely viscous materials, δ=90° (stress leadsthe strain by 90° although the stress is in phase with the strain rate).For viscoelastic materials, 0 <δ<90. The shear thinning slope (STS) wasmeasured using plots of the logarithm (base ten) of the dynamicviscosity versus logarithm (base ten) of the frequency. The slope is thedifference in the log(dynamic viscosity) at a frequency of 100 s⁻¹ andthe log(dynamic viscosity) at a frequency of 0.01 s⁻¹ divided by 4.Dynamic viscosity is also referred to as complex viscosity or dynamicshear viscosity.

The dynamic shear viscosity (η*) versus frequency (ω) curves were fittedusing the Cross model (see, for example, C. W. Macosco, RHEOLOGY:PRINCIPLES, MEASUREMENTS, AND APPLICATIONS, Wiley-VCH, 1994):

$\eta^{*} = \frac{\eta_{0}}{1 + ({\lambda\omega})^{1 - n}}$

The three parameters in this model are: the zero-shear viscosity; λ, theaverage relaxation time; and n, the power-law exponent. The zero-shearviscosity is the value at a plateau in the Newtonian region of the flowcurve at a low frequency, where the dynamic viscosity is independent offrequency. The average relaxation time corresponds to the inverse of thefrequency at which shear-thinning starts. The power-law exponentdescribes the extent of shear-thinning, in that the magnitude of theslope of the flow curve at high frequencies approaches 1−n on alog(η*)-log(ω) plot. For Newtonian fluids, n=1 and the dynamic complexviscosity is independent of frequency. For the polymers of interesthere, n<1, so that enhanced shear-thinning behavior is indicated by adecrease in n (increase in 1-n).

The transient uniaxial extensional viscosity was measured using aSER-2-A Testing Platform available from Xpansion Instruments LLC,Tallmadge, Ohio, USA. The SER Testing Platform was used on a RheometricsARES-LS (RSA3) strain-controlled rotational rheometer available from TAInstruments Inc., New Castle, Del. USA. The SER Testing Platform isdescribed in U.S. Pat. Nos. 6,578,413 & 6,691,569, which areincorporated herein for reference. A general description of transientuniaxial extensional viscosity measurements is provided, for example, in“Strain hardening of various polyolefins in uniaxial elongational flow”,The Society of Rheology, Inc., J. Rheol. 47(3), 619-630 (2003); and“Measuring the transient extensional rheology of polyethylene meltsusing the SER universal testing platform”, The Society of Rheology,Inc., J. Rheol. 49(3), 585-606 (2005), incorporated herein for referenceStrain hardening occurs when a polymer is subjected to uniaxialextension and the transient extensional viscosity increases more thanwhat is predicted from linear viscoelastic theory. Strain hardening isobserved as abrupt upswing of the extensional viscosity in the transientextensional viscosity vs. time plot. A strain hardening ratio (SHR) isused to characterize the upswing in extensional viscosity and is definedas the ratio of the maximum transient extensional viscosity over threetimes the value of the transient zero-shear-rate viscosity at the samestrain. Strain hardening is present in the material when the ratio isgreater than 1.

Complex viscosity is determined as described in the Experimental sectionof U.S. Pat. No. 9,458,310. Also see M. Van Gurp, J. Palmen, Rheol.Bull., 1998, 67, 5-8. The dependence of complex viscosity as a functionof frequency can also be determined from rheological measurements at190° C. The following ratio:

[η*(0.1 rad/s)−η*(100 rad/s)]η*(0.1 rad/s)

was used to measure the degree of shear thinning of the polymericmaterials of the embodiments herein, where η*(0.1 rad/s) and η*(100rad/s) are the complex viscosities at frequencies of 0.1 and 100 rds,respectively, measured at 190° C. The higher this ratio, the higher isthe degree of shear thinning.

The transient uniaxial extensional viscosity was measured using aSER-2-A Testing Platform available from Xpansion Instruments LLC,Tallmadge, Ohio, USA. The SER Testing Platform was used on a RheometricsARES-LS (RSA3) strain-controlled rotational rheometer available from TAInstruments Inc., New Castle, Del., USA. The SER Testing Platform isdescribed in U.S. Pat. No. 6,578,413 and U.S. Pat. No. 6,691,569, whichare incorporated herein for reference. A general description oftransient uniaxial extensional viscosity measurements is provided, forexample, in “Strain hardening of various polyolefins in uniaxialelongational flow”, The Society of Rheology, Inc., J. Rheol. 47(3),619-630 (2003) and “Measuring the transient extensional rheology ofpolyethylene melts using the SER universal testing platform”, TheSociety of Rheology, Inc., J. Rheol. 49(3), 585-606 (2005), incorporatedherein for reference. Strain hardening occurs when a polymer issubjected to uniaxial extension and the transient extensional viscosityincreases more than what is predicted from linear viscoelastic theory.Strain hardening is observed as abrupt upswing of the extensionalviscosity in the transient extensional viscosity vs. time plot. A strainhardening ratio (SHR) is used to characterize the upswing in extensionalviscosity and is defined as the ratio of the maximum transientextensional viscosity over three times the value of the transientzero-shear-rate viscosity at the same strain. Strain hardening ispresent in the material when the ratio is greater than 1.

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents and/or testing procedures to the extent they arenot inconsistent with this text. As is apparent from the foregoinggeneral description and the specific embodiments, while forms of theinvention have been illustrated and described, various modifications canbe made without departing from the spirit and scope of the invention.Accordingly, it is not intended that the invention be limited thereby.Likewise, the term “comprising” is considered synonymous with the term“including.” Likewise whenever a composition, an element or a group ofelements is preceded with the transitional phrase “comprising,” it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of,” “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

What is claimed is:
 1. A process to produce branched ethylene copolymerscomprising: 1) contacting monomer comprising ethylene, C₄ to C₈alpha-olefin comonomer with a catalyst system comprising an activator, ametal hydrocarbenyl chain transfer agent, and one or more catalystcomplexes represented by the Formulae I and II;

wherein: M is a Group 3, 4, 5, 6, 7, 8, 9, or 10 metal; E is chosen fromC(R²) or C(R³)(R³′); X is an anionic leaving group; L is a neutral Lewisbase; R¹ and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups; R² is a groupcontaining 1-10 carbon atoms that is optionally joined with R⁴ to forman aromatic ring; R³, R³′, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² areeach independently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphino; J is a divalent group that forms athree-atom-length bridge between the pyridine ring and the amidonitrogen; n is 1 or 2; m is 0, 1, or 2; two X groups optionally jointogether to form a dianionic group; two L groups optionally jointogether to form a bidentate Lewis base; an X group optionally join toan L group to form a monoanionic bidentate group; adjacent groups fromthe following R³, R³′, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² may bejoined to form a ring; where the metal hydrocarbenyl chain transferagent is one or more aluminum vinyl transfer agents, AVTA, representedby Formula:Al(R′)_(3−v)(R″)_(v) wherein each R′, independently, is a C₁-C₃₀hydrocarbyl group; each R″, independently, is a C₄-C₂₀ hydrocarbenylgroup having an end-vinyl group; and v is from 0.1 to 3; and 2)obtaining branched ethylene copolymers comprising greater than 50 mol %ethylene, one or more C₄ to C₈ alpha-olefin comonomers, and a remnant ofthe metal hydrocarbenyl chain transfer agent, wherein said branchedethylene copolymer: a) has a g′_(vis) of less than 0.97; b) isessentially gel free (such as 5 wt % or less of xylene insolublematerial); c) has an Mw of 60,000 g/mol or more; and d) has a Mw/Mn ofless than 4.0.
 2. A process to produce branched copolymerscomprising: 1) contacting monomer comprising ethylene, C₄ to C₈alpha-olefin comonomers with a catalyst system comprising an activator,a metal hydrocarbenyl chain transfer agent, and one or more catalystcomplexes represented by the Formula (6):

wherein (1) M is a group 4 metal, preferably hafnium; (2) N is nitrogen;(3) L⁷ is a group that links R⁵⁰ to Z′ by a three atom bridge with thecentral of the three atoms being a group 15 or 16 element thatpreferably forms a dative bond to M, and is a C₅-C₂₀ heteroaryl groupcontaining a Lewis base functionality, especially a divalent pyridinyl,substituted pyridinyl, quinolinyl, or substituted quinolinyl group; (4)Z′ is a divalent linker group, (R⁵⁶)_(p)C—C(R⁵⁷)_(q), where R⁵⁶ and R⁵⁷are independently selected from the group consisting of hydrogen,hydrocarbyls, substituted hydrocarbyls, and wherein adjacent R⁵⁶ and R⁵⁷groups may be joined to form an aromatic or saturated, substituted orunsubstituted hydrocarbyl ring, wherein the ring has 5, 6, 7, or 8 ringcarbon atoms and where the substituents on the ring can join to formadditional rings, and p is 1 or 2 and q is 1 or 2; (5) R⁵⁰ and R⁵³ areeach, independently, ER⁵⁴R⁵⁵ with E being carbon, silicon or germanium,and each R⁵⁴ and R⁵⁵ being independently selected from the groupconsisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy,silyl, amino, aryloxy, halogen and phosphino, and R⁵⁴ and R⁵⁵ may bejoined to form a saturated heterocyclic ring, or a saturated substitutedheterocyclic ring where substitutions on the ring can join to formadditional rings; (6) R⁵¹ and R⁵² are independently selected from thegroup consisting of hydrocarbyls, substituted hydrocarbyls, silylcarbylsand substituted silylcarbyl groups; and (7) each X is independently aunivalent anionic ligand, or two Xs are joined and bound to the metalatom to form a metallocycle ring, or two Xs are joined to form achelating ligand, a diene ligand, or an alkylidene ligand; where themetal hydrocarbenyl chain transfer agent is one or more aluminum vinyltransfer agents, AVTA, represented by Formula:Al(R′)_(3−v)(R″)_(v) wherein each R′, independently, is a C₁-C₃₀hydrocarbyl group; each R″, independently, is a C₄-C₂₀ hydrocarbenylgroup having an end-vinyl group; and v is from 0.1 to 3; and 2)obtaining branched ethylene copolymers comprising greater than 50 mol %ethylene, one or more C₂ to C₈ alpha-olefin comonomers, and a remnant ofthe metal hydrocarbenyl chain transfer agent, wherein said branchedethylene copolymer: a) has a g′_(vis) of less than 0.97; b) isessentially gel free (such as 5 wt % or less of xylene insolublematerial); c) has an Mw of 60,000 g/mol or more; and d) has a Mw/Mn ofless than 4.0.
 3. The process of claim 1, wherein the catalyst complexis represented by the Formula:

wherein: M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal; E isselected from carbon, silicon, or germanium; X is an anionic group; L isa neutral Lewis base; R¹ and R¹³ are each independently selected fromthe group consisting of hydrocarbyls, substituted hydrocarbyls, andsilyl groups; R² through R¹² are each independently selected from thegroup consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino,aryloxy, substituted hydrocarbyls, halogen, and phosphino; n is 1 or 2;m is 0, 1, or 2; two X groups may be joined together to form a dianionicgroup; two L groups may be joined together to form a bidentate Lewisbase; an X group may be joined to an L group to form a monoanionicbidentate group; R⁷ and R⁸ may be joined to form a ring; and R¹⁰ and R¹¹may be joined to form a ring.
 4. The process of claim 1, wherein thecatalyst complex is represented by the Formula (Ia) or (IIa):

wherein: M is a Group 3, 4, 5, 6, 7, 8, 9, or 10 metal; J is athree-atom-length bridge between the quinoline and the amido nitrogen;E* is selected from carbon, silicon, or germanium; X is an anionicleaving group; L is a neutral Lewis base; R¹ and R¹³ are independentlyselected from the group consisting of hydrocarbyls, substitutedhydrocarbyls, and silyl groups; R²* through R¹² are independentlyselected from the group consisting of hydrogen, hydrocarbyls, alkoxy,silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;n is 1 or 2; m is 0, 1, or 2 n+m is not greater than 4; any two adjacentR groups (e.g., R¹ & R², R² & R³, etc.) may be joined to form asubstituted or unsubstituted hydrocarbyl or heterocyclic ring, where thering has 5, 6, 7, or 8 ring atoms and where substitutions on the ringcan join to form additional rings; any two X groups may be joinedtogether to form a dianionic group; any two L groups may be joinedtogether to form a bidentate Lewis base; and an X group may be joined toan L group to form a monoanionic bidentate group.
 5. The process ofclaim 1, wherein M is Ti, Zr, or Hf.
 6. The process of claim 1, whereinE is carbon.
 7. A process to produce ethylene copolymers comprising: 1)contacting monomer comprising ethylene, a C₄ to C₈ alpha-olefincomonomers with a catalyst system comprising an activator, a metalhydrocarbenyl chain transfer agent, and one or more catalyst complexesrepresented by the Formula:

wherein: M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal; E isselected from carbon, silicon, or germanium; X is an anionic group; L isa neutral Lewis base; R¹ and R¹³ are each independently selected fromthe group consisting of hydrocarbyls, substituted hydrocarbyls, andsilyl groups; R⁵ through R¹² and R¹⁴ through R¹⁶ are each independentlyselected from the group consisting of hydrogen, hydrocarbyls, alkoxy,silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino;n is 1 or 2; m is 0, 1, or 2; two X groups may be joined together toform a dianionic group; two L groups may be joined together to form abidentate Lewis base; an X group may be joined to an L group to form amonoanionic bidentate group; R⁷ and R⁸ may be joined to form a ring; R¹⁰and R¹¹ may be joined to form a ring; where the metal hydrocarbenylchain transfer agent is one or more aluminum vinyl transfer agents,AVTA, represented by Formula:Al(R′)_(3−v)(R″)_(v) wherein each R′, independently, is a C₁-C₃₀hydrocarbyl group; each R″, independently, is a C₄-C₂₀ hydrocarbenylgroup having an end-vinyl group; and v is from 0.1 to 3; and 2)obtaining branched ethylene copolymers comprising greater than 50 mol %ethylene, one or more C₄ to C₈ alpha-olefin comonomers, and a remnant ofthe metal hydrocarbenyl chain transfer agent, wherein said branchedethylene copolymer: a) has a g′_(vis) of less than 0.97; b) isessentially gel free (such as 5 wt % or less of xylene insolublematerial); c) has an Mw of 60,000 g/mol or more; and d) has a Mw/Mn ofless than 4.0.
 8. The process of claim 1, wherein the activatorcomprises an alumoxane and or a non-coordinating anion, preferably theactivator comprises one or more of: trimethylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄⁻], 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine,triphenylcarbenium tetraphenylborate, and triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate.
 9. The process of claim 1,wherein v is from 0.1 to
 3. 10. The process of claim 1, wherein R″ isbutenyl, pentenyl, heptenyl, octenyl, or decenyl and/or wherein R′ ismethyl, ethyl, propyl, isobutyl, or butyl.
 11. The process of claim 1,wherein the aluminum vinyl transfer agent comprises one or more oftri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum,tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum,tri(dec-9-en-1-yl)aluminum, dimethyl (oct-7-en-1-yl)aluminum,diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum,diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum,diisobutyl(dec-9-en-1-yl)aluminum, diisobutyl(dodec-11-en-1-yl)aluminum,methyl-di(oct-7-en-1-yl)aluminum, ethyl-di(oct-7-en-1-yl)aluminum,butyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(oct-7-en-1-yl)aluminum,isobutyl-di(non-8-en-1-yl)aluminum, isobutyl-di(dec-9-en-1-yl)aluminum,and isobutyl-di(dodec-11-en-1-yl)aluminum.
 12. The process of claim 1,wherein v=2.
 13. The process of claim 1, wherein the comonomer comprises1-butene, 1-hexene and/or 1-octene.
 14. The process of claim 1, whereinthe comonomer comprises 1-hexene.
 15. The process of claim 1, whereinthe catalyst complex is supported.
 16. A ethylene copolymer comprisingat least 50 mol % or more ethylene, 50 mol % or less of a C₄ to C₈alpha-olefin comonomer, and a remnant of a metal hydrocarbenyl chaintransfer agent wherein the metal hydrocarbenyl chain transfer agent isrepresented by Formula:Al(R′)_(3−v)(R″)_(v) wherein each R′, independently, is a C₁-C₃₀hydrocarbyl group; each R″, independently, is a C₄-C₂₀ hydrocarbenylgroup having an end-vinyl group; and v is from 0.1 to 3; wherein saidbranched ethylene copolymer: a) has a g′_(vis) of less than 0.97; b) isessentially gel free (such as 5 wt % or less of xylene insolublematerial); c) has an Mw of 60,000 g/mol or more; and d) has a Mw/Mn ofless than 4.0.
 17. The copolymer of claim 16, wherein said branchedethylene copolymer has a g′_(vis) of less than 0.90, alternately lessthan 0.85.
 18. The copolymer of claim 16, wherein said branched ethylenecopolymer has a complex viscosity of at least 500 Pa·s measured at 0.1rad/sec and a temperature of 190° C., alternately at least 5000 Pa·s.19. The copolymer of claim 16, wherein the copolymer comprises from 0.5to 30 mol % of one or more C₄ to C₈ alpha-olefin comonomers, and 0.001to 10 mol % of the remnant of the metal hydrocarbenyl chain transferagent.
 20. The copolymer of claim 16, wherein the comonomer is one ormore of 1-butene, 1-hexene and 1-octene.
 21. The copolymer of claim 16,wherein the comonomer is 1-hexene.
 22. The process of claim 1, whereinsaid branched ethylene copolymer has a complex viscosity of at least 500Pa·s measured at 0.1 rad/sec and a temperature of 190° C., alternatelyat least 5000 Pa·s.